Solid polyelectrolyte, assembly of membrane and electrodes, and fuel cell

ABSTRACT

An object of the present invention is to provide a highly durable solid polymer electrolyte that has a deterioration resistance equal to or higher than that of the fluorine-containing solid polymer electrolytes or a deterioration resistance sufficient for practical purposes, and can be produced at a low cost. According to the present invention, there is provided a solid polymer electrolyte comprising a polyether ether sulfone that is used as a electrolyte and has sulfoalkyl groups bonded to its aromatic rings and represented by the general formula —(CH 2 ) n —SO 3 H.

BACKGROUND OF THE INVENTION

The present invention relates to a solid polymer electrolyte membraneused in fuel cells, water electrolysis, hydrogen halide acidelectrolysis, sodium chloride electrolysis, oxygen concentrators,moisture sensors, gas sensors, etc.; an electrocatalyst-coatingsolution; an assembly of said membrane and electrodes; and fuel cells.

Solid polymer electrolytes are solid polymeric materials having groupscharacteristic of the electrolytes (e.g. sulfonic acid groups) in thepolymer chain. Since they bind strongly to specific ions or areselectively permeable to cations or anions, they are utilized forvarious purposes after being molded or shaped into particles, fiber or amembrane. For example, they are utilized in electrodialysis, diffusedialysis, diaphragms for cell, etc.

In a reformed-gas fuel cell, an electromotive force is obtained byproviding a pair of electrodes on both sides, respectively, of aproton-conductive solid polymer electrolyte membrane, supplying hydrogengas obtained by reforming a low-molecular weight hydrocarbon such asmethane, methanol or the like to one of the electrodes (a hydrogenelectrode) as a fuel gas, and supplying oxygen gas or air to the otherelectrode (an oxygen electrode) as an oxidizing agent. In waterelectrolysis, hydrogen and oxygen are produced by electrolyzing water bythe use of a solid polymer electrolyte membrane.

As a solid polymer electrolyte membrane for a fuel cell, waterelectrolysis or the like, fluorine-containing solid polymer electrolytemembranes represented by perfluorocarbon sulfonic acid solid polymerelectrolyte membranes with a high proton conductivity known by theirtrade names of Nafion® (a registered trade name, mfd. by E.I. du Pont deNemours & Co.), Aciplex® (a registered trade name, ASAHI ChemicalIndustry Co., Ltd.) and Flemion® (a trade name, mfd. by Asahi Glass Co.,Ltd.) are used because of their excellent chemical stability.

In sodium chloride electrolysis, sodium hydroxide, chlorine and hydrogenare produced by electrolyzing an aqueous sodium chloride solution by theuse of a solid polymer electrolyte membrane.

In this case, since the solid polymer electrolyte membrane is exposed tochlorine and an aqueous sodium hydroxide solution of high temperatureand concentration, a hydrocarbon solid polymer electrolyte membranehaving a low resistance to chlorine and the solution cannot be used.Therefore, as a solid polymer electrolyte membrane for sodium chlorideelectrolysis, there is generally used a perfluorocarbon sulfonic acidsolid polymer electrolyte membrane which is resistant to chlorine andthe aqueous sodium hydroxide solution of high temperature andconcentration and has carboxylic acid groups introduced partly into themembrane surface in order to prevent the reverse diffusion of ionsgenerated.

The fluorine-containing solid polymer electrolyte membranes representedby the perfluorocarbon sulfonic acid solid polymer electrolyte membraneshave a very high chemical stability because of their C—F bonds and henceare used not only as a solid polymer electrolyte membrane for theabove-mentioned fuel cell, water electrolysis or sodium chlorideelectrolysis but also as a solid polymer electrolyte membrane forhydrogen halide acid electrolysis. In addition, they are widely utilizedin moisture sensors, gas sensors, oxygen concentrators, etc. by takingadvantage of their proton conductivity.

The fluorine-containing solid polymer electrolyte membranes, however,are disadvantageous in that they are difficult to produce and are veryexpensive. Therefore, the fluorine-containing solid polymer electrolytemembranes are used for special purposes, for example, they are used insolid polymer membrane fuel cells for space research or military use.Thus, they have been difficult to use for livelihood in, for example, asolid polymer membrane fuel cell as a low-pollution power source forautomobile.

As inexpensive solid polymer electrolyte membranes, the followingaromatic hydrocarbon solid polymer electrolyte membranes, for example,have been proposed. JP-A-6-93114 has proposed a sulfonated polyetherether ketone membrane. JP-A-9-245818 and JP-A-11-116679 have proposedsulfonated polyether sulfone membranes. JP-A-11-67224 has proposed asulfonated polyether ether sulfone membrane. JP-A-10-503788 has proposeda sulfonated acrylonitrile-butadiene-styrene polymer membrane.JP-A-11-510198 has proposed a sulfonated polysulfide membrane.JP-A-11-515040 has proposed a sulfonated polyphenylene membrane.

These aromatic hydrocarbon solid polymer electrolyte membranes obtainedby sulfonating engineering plastics are advantageous in that theirproduction is easier and entails a lower cost as compared with theproduction of the fluorine-containing solid polymer electrolytemembranes represented by Nafion®.

The sulfonated aromatic hydrocarbon solid polymer electrolyte membranes,however, are disadvantageous in that they tend to be deteriorated.According to JP-A-2000-106203, a solid polymer electrolyte membranehaving an aromatic hydrocarbon skeleton tends to be deteriorated becausehydrogen peroxide produced in a catalyst layer formed on the boundarysurface between the solid polymer electrolyte membrane and an oxygenelectrode oxidizes and deteriorates the aromatic hydrocarbon skeleton.

Therefore, for example, JP-9-102322 has proposed a sulfonatedpolystyrene-grafted ethylene-tetrafluoroethylene copolymer (ETFE)membrane comprising a main chain formed by the copolymerization of afluorocarbon type vinyl monomer and a hydrocarbon type vinyl monomer andhydrocarbon side chains having sulfonic acid groups, as a solid polymerelectrolyte membrane which has an oxidative-deterioration resistanceequal to or higher than that of the fluorine-containing solid polymerelectrolyte membranes and can be produced at a low cost.

The sulfonated polystyrene-grafted ETFE membrane disclosed inJP-A-9-102322 is reported as follows: it is inexpensive, has asufficient strength as solid polymer electrolyte membrane for a fuelcell, and can be improved in electric conductivity by increasing theamount of sulfonic acid groups introduced.

However, in the sulfonic acid type polystyrene-grafted ETFE membrane,the main chain portion formed by the copolymerization of a fluorinatedvinyl monomer and a vinyl monomer has a high resistance to oxidativedeterioration, but the side chain portion having sulfonic acid groupsintroduced thereinto is an aromatic hydrocarbon polymer which is subjectto oxidative deterioration. Therefore, said membrane is disadvantageousin that when the membrane is used in a fuel cell, the resistance tooxidative deterioration of the whole membrane is not sufficient,resulting in a low durability.

U.S. Pat. No. 4,012,303 and U.S. Pat. No. 4,605,685 have proposedsulfonic acid type poly(trifluorostyrene)-grafted ETFE membranesobtained by graft-copolymerizing α,β,β-trifluorostyrene onto a membraneproduced by the copolymerization of a fluorinated vinyl monomer and avinyl monomer, and introducing sulfonic acid groups into theα,β,β-trifluorostyrene units to obtain a solid polymer electrolytemembrane.

These membranes are obtained by using α,β,β-trifluorostyrene prepared bypartial fluorination of styrene, in place of styrene on the assumptionthat the chemical stability of the above-mentioned polystyrene sidechain portion having sulfonic acid groups introduced thereinto is notsufficient. The synthesis of α,β,β-trifluorostyrene as a startingmaterial for the side chain portion, however, is difficult. Therefore,when said membranes are used as a solid polymer electrolyte membrane fora fuel cell, there is a cost problem as in the case of theabove-mentioned Nafion®.

Moreover, α,β,β-trifluorostyrene is disadvantageous in that because ofits low polymerizability, the amount of α,β,β-trifluorostyreneintroducible as grafted side chains is small, so that the resultingmembrane has a low electric conductivity.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a highly durable solidpolymer electrolyte which has a deterioration resistance equal to orhigher than that of the fluorine-containing solid polymer electrolytesor a deterioration resistance sufficient for practical purposes, and canbe produced at a low cost.

The present inventors investigated in detail the mechanism ofdeterioration of a solid polymer electrolyte membrane. Consequently, thefollowing was found: in an aqueous solution, an aromatic sulfonic acidhaving one or more sulfonic acid groups directly bonded to the aromaticring is in such a state that the aromatic ring and sulfuric acid are indissociation equilibrium; and with a decrease of the sulfuric acidconcentration and a rise of the temperature, the sulfonic acid group(s)is more liable to be released from the aromatic sulfonic acid.

That is, it was found that shortening of the lifetime of a fuel cellusing an aromatic hydrocarbon solid polymer electrolyte membrane iscaused not by the oxidative deterioration of the membrane itself whichhas been regarded as a cause, but by the following phenomenon: underconditions for the fuel cell, the sulfuric acid concentration is low, sothat the sulfonic acid groups are released from the aromatic ring,resulting in a lowered ionic conductance.

For the achievement of the above object, the highly durable solidpolymer electrolyte of the present invention is characterized bycomprising a polyether ether sulfone having sulfonic acid groups eachintroduced thereinto through an alkylene group as shown in the formula[1]:—(CH₂ )_(n)—SO₃H  [1]wherein n is an integer of 1 to 6. Thus, it becomes possible to obtain ahighly durable solid polymer electrolyte which has a durability equal toor higher than that of the fluorine-containing solid polymerelectrolytes or a durability sufficient for practical purposes, and isinexpensive.

A solid polymer electrolyte having sulfonic acid groups introducedthereinto through alkylene groups is advantageous in that its ionelectric conductivity is higher than that of a solid polymer electrolytehaving sulfonic acid groups introduced thereinto without an alkylenegroup, when these solid polymer electrolytes have the same ion-exchangegroup equivalent weight. It is conjectured that the higher ion electricconductivity is concerned with the fact that the sulfonic acid groupsintroduced through alkylene groups are more mobile than the sulfonicacid groups introduced without an alkylene group.

A solid polymer electrolyte obtained when n in the above formula [1] is3 to 6 is preferable because its ionic conductance is higher than thatof a solid polymer electrolyte obtained when n is 1 or 2. The reason forthis phenomenon is guessed as follows: when the value of n is increased,SO₃H becomes mobile, so that the resulting solid polymer electrolytetends to have a cohesion structure or an ion channel structure.

A characteristic of the present invention is that a polyether ethersulfone having sulfoalkyl groups of the above formula [1] bonded theretois used as an electrolyte.

Another characteristic of the present invention is that there is used asan electrolyte a polyether ether sulfone having sulfonic acid groupsbonded thereto through alkylene groups which is represented by any ofthe formulas [2] to [9] exhibited hereinafter.

Further another characteristic of the present invention is that theabove-mentioned sulfonic acid groups are bonded so that the sulfonicacid group equivalent weight may be 530 to 970 g/equivalent.

Still another characteristic of the present invention is that theabove-mentioned electrolyte is used as an electrolyte membrane.

Still another characteristic of the present invention is anelectrocatalyst-coating solution containing the above-mentioned solidpolymer electrolyte.

Still another characteristic of the present invention is amembrane-electrodes assembly comprising the above-mentioned solidpolymer electrolyte membrane and a pair of electrodes, i.e., an oxygenelectrode and a hydrogen electrode which are located on both sides,respectively, of said solid polymer electrolyte membrane.

Still another characteristic of the present invention is amembrane-electrodes assembly comprising a solid polymer electrolytemembrane obtained by the use of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups which isrepresented by any of the formulas [1] to [9] exhibited hereinafter,said solid polymer electrolyte membrane being coated with theabove-mentioned electrocatalyst-coating solution, and a pair ofelectrodes, i.e., an oxygen electrode and a hydrogen electrode which arelocated on both sides, respectively, of said solid polymer electrolytemembrane.

Still another characteristic of the present invention is amembrane-electrodes assembly wherein the above-mentionedelectrocatalyst-coating solution is Nafion (a perfluorocarbon sulfonicacid solid polymer electrolyte solution, a registered trade name, mfd.by E.I. du Pont de Nemours & Co.).

Still another characteristic of the present invention is a solid polymerelectrolyte fuel cell comprising a membrane-electrodes assemblycomprising the above-mentioned solid polymer electrolyte membrane and apair of electrodes, i.e., an oxygen electrode and a hydrogen electrodewhich are located on both sides, respectively, of said solid polymerelectrolyte membrane; a pair of supporting current collectors providedon both sides, respectively, of said membrane-electrodes assembly; andseparators located at the peripheries of said supporting currentcollectors, respectively.

Other objects, features and advantages of the invention will becomeapparent from the following description of the embodiments of theinvention taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic perspective view showing the structure of a singlecell for the solid polymer electrolyte fuel cell of the presentinvention produced in Example 1.

FIG. 2 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 1.

FIG. 3 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 2.

FIG. 4 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 3.

FIG. 5 is a current density-voltage graph showing the output capabilityof a single cell for solid polymer electrolyte fuel cell produced inExample 4.

FIG. 6 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 4.

FIG. 7 is a current density-voltage graph showing the output capabilityof a single cell for solid polymer electrolyte fuel cell produced inExample 10.

FIG. 8 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 10.

FIG. 9 is a current density-voltage graph showing the output capabilityof a single cell for solid polymer electrolyte fuel cell produced inExample 11.

FIG. 10 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 11.

FIG. 11 is a current density-voltage graph showing the output capabilityof a single cell for solid polymer electrolyte fuel cell produced inExample 12.

FIG. 12 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 12.

FIG. 13 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 13.

FIG. 14 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 14.

FIG. 15 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 15.

FIG. 16 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 16.

FIG. 17 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 17.

FIG. 18 is a graph showing the results of a durability test on singlecells for solid polymer electrolyte fuel cell produced in Example 18.

DESCRIPTION OF REFERENCE NUMERALS

1—solid polymer electrolyte membrane, 2—air electrode, 3—oxygenelectrode, 4—membrane-electrodes assembly, 5—supporting currentcollector, 6—separator, 7—air, 8—air+water, 9—hydrogen+water,10—residual hydrogen, 11—water.

DETAILED DESCRIPTION OF THE INVENTION

The present inventive polyether ether sulfone solid polymer electrolytehaving sulfonic acid groups introduced thereinto through alkylene groupsis preferably a polyether ether sulfone solid polymer electrolyte havingsulfonic acid groups introduced thereinto through alkylene groups whichis represented by the formula [2]:

wherein n is an integer of 1 to 6, each of m, a and b is an integer of 0to 4, provided that m, a and b are not 0 at the same time, x is aninteger of 1 to 3, y is an integer of 1 to 5, and Ar is an aromaticresidue.

Specific examples of the solid polymer electrolyte of the presentinvention are polyether ether sulfone solid polymer electrolytes havingsulfonic acid groups introduced thereinto through alkylene groups whichare represented by the formulas [3] to [8]:

wherein n is an integer of 1 to 6, and each of a, b, c and d is aninteger of 0 to 4, provided that b, c and d are not 0 at the same time.

wherein each of a, b, c and d is an integer of 0 to 4, provided that a,b, c and d are not 0 at the same time.

wherein each of a, b, c and d is an integer of 0 to 4, provided that a,b, c and d are not 0 at the same time.

wherein n is an integer of 1 to 6, and each of a, b and c is an integerof 0 to 4, provided that a, b and c are not 0 at the same time.

wherein each of a, b and c is an integer of 0 to 4, provided that a, band c are not 0 at the same time.

wherein each of a, b and c is an integer of 0 to 4, provided that a, band c are not 0 at the same time.

wherein each of a, b, c and d is an integer of 0 to 4, provided that a,b, c and d are not 0 at the same time.

A method for introducing sulfonic acid groups into a polyether ethersulfone or its polymer alloy through alkylene groups is not particularlylimited. A specific example of the introduction method is a method ofintroducing a sulfonic acid group into an aromatic ring by the use ofthe sultone shown in the scheme (I) as described in J. Amer. Chem. Soc.,76, 5357-5360 (1954):

wherein m is 1 or 2.

Other specific examples of the introduction method are a method ofreplacing a hydrogen atom in an aromatic ring with a lithium atom,replacing the lithium atom with a halogenoalkylene group by the use of adihalogenoalkane, and converting the halogenoalkylene group to introducea sulfonic acid group through an alkylene group; and a method ofintroducing a halogenobutyl group into the substituted aromatic ringhaving the lithium atom as the substituent, by the use of atetramethylenehalogenium ion and converting the halogen to a sulfonicacid group.

wherein n is an integer of 1 to 6, and x is a halogen atom.

All the reactions for introducing a sulfonic acid group into an aromaticring through an alkylene group are electrophilic reactions with thearomatic ring. A polyether ether sulfone having the structure accordingto the present invention in which the electron density of aromatic ringsis high is desirable because the reaction takes place under relativelymild conditions as compared with other engineering plastics.

Although a method for introducing sulfonic acid groups into a polyetherether sulfone through alkylene groups is not particularly limited, amethod involving a small number of synthesis steps, such as the methodshown by the above scheme (I) is preferable from the viewpoint of cost.

The solid polymer electrolyte used in the present invention is a polymerhaving sulfonic acid groups introduced thereinto through alkylene groupswhich has an ion-exchange group equivalent weight of 250 to 2,500g/equivalent. The ion-exchange group equivalent weight is preferably 300to 1,500 g/equivalent, more preferably 530 to 970 g/equivalent. When theion-exchange group equivalent weight is more than 2,500 g/equivalent,the output capability is undesirably deteriorated in some cases. Whenthe ion-exchange group equivalent weight is less than 250 g/equivalent,the water resistance of the polymer is undesirably deteriorated.

The term “ion-exchange group equivalent weight” used herein means themolecular weight of the polymer having sulfonic acid groups introducedthereinto through alkylene groups, per unit equivalent of the sulfonicacid groups introduced through the alkylene groups. The smaller theion-exchange group equivalent weight, the higher the degree ofintroduction of the sulfonic acid groups introduced through the alkylenegroups. The ion-exchange group equivalent weight can be measured by¹H-NMR spectroscopy, elemental analysis, the acid-base titrationdisclosed in the specification of JP-B-1-52866, nonaqueous acid-basetitration (normal solution: a solution of potassium methoxide inbenzene-methanol) or the like.

As to a method for controlling the ion-exchange group equivalent weightof said solid polymer electrolyte having sulfonic acid groups introducedthereinto through alkylene groups, at 250 to 2,500 g/equivalent, apolymer that has sulfonic acid groups introduced thereinto throughalkylene groups and has a desirable ion-exchange group equivalent weightcan be obtained by varying the blending ratio of an aromatic hydrocarbonpolymer to a sulfoalkylating agent, the reaction temperature, thereaction time, a solvent for reaction, etc.

When used in a fuel cell, the solid polymer electrolyte used in thepresent invention is usually used in the form of a membrane. A methodfor forming the polymer having sulfonic acid groups introduced thereintothrough alkylene groups into the membrane is not particularly limited.As the method, there can be adopted, for example, a method of forming afilm from the polymer in a solution state (a solution cast method) and amethod of forming a film from the polymer in a molten state (a meltpressing method or a melt extrusion method). Specifically, in the formermethod, a film is formed by applying a polymer solution on a glass plateby casting, and removing the solvent.

The solvent used for the film formation is not particularly limited andmay be any solvent so long as it permits dissolution of the polymertherein and can be removed after the application. As the solvent, therecan be suitably used aprotic polar solvents such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,dimethyl sulfoxide etc.; alkylene glycol monoalkyl ethers such asethylene glycol monomethyl ether, ethylene glycol monoethyl ether,propylene glycol monomethyl ether, propylene glycol monoethyl ether,etc.; halogen-containing solvents such as dichloromethane,trichloroethane, etc.; and alcohols such as 1-propyl alcohol, t-butylalcohol, etc.

Although the thickness of the solid polymer electrolyte membrane is notparticularly limited, it is preferably 10 to 200 μm, in particular, 30to 100 μm. For attaining a film strength sufficient for practicalpurposes, the thickness is preferably more than 10 μm. For reducing theresistance of the membrane, namely, improving the power-generatingcapability, the thickness is preferably less than 200 μm. When thesolution cast method is adopted, the film thickness can be controlled byadjusting the concentration of the solution or the coating thickness ona substrate. When a film is formed from the polymer in a molten state,the film thickness can be controlled by stretching a film with apredetermined thickness obtained by the melt pressing method or meltextrusion method, by a predetermined factor.

In the production of the solid polymer electrolyte of the presentinvention, additives (e.g. plasticizers, stabilizers and mold releaseagents) used in conventional polymers may be used so long as the objectof the present invention is not affected.

When the solid polymer electrolyte membrane is used in a fuel cell,electrodes used in an assembly of the membrane and the electrodes arecomposed of an electroconductive material supporting thereon fineparticles of a catalyst metal and may, if necessary, contain waterrepellents and binders. A layer composed of an electroconductivematerial supporting no catalyst thereon and optionally a repellent and abinder may be formed on the outer surface of a catalyst layer.

As the catalyst metal used in the electrodes, any metal may be used solong as it accelerates the oxidation of hydrogen and the reduction ofoxygen. The catalyst metal includes, for example, platinum, gold,silver, palladium, iridium, rhodium, ruthenium, iron, cobalt, nickel,chromium, tungsten, manganese, vanadium, and alloys thereof.

Of these catalysts, in particular, platinum is often used. The particlesize of the metal used as the catalyst is usually 10 to 300 angstrom.The adhesion of such a catalyst to a carrier such as carbon reduces theamount of the catalyst used and hence is advantageous from the viewpointof cost. The amount of the catalyst supported is preferably 0.01 to 10mg/cm² in the electrodes formed.

As the electroconductive material, any material may be used so long asit is an electronically conductive substance. The electroconductivematerial includes, for example, various metals and carbon materials.

The carbon materials include, for example, carbon blacks (e.g. furnaceblack, channel black and acetylene black), activated carbon, andgraphite. These may be used singly or as a mixture thereof.

As the water repellent, carbon fluoride, for example, is used. As thebinder, the electrocatalyst-coating solution of the present invention ispreferably used as it is from the viewpoint of adhesion, though othervarious resins may be used. As these resins, water-repellentfluorine-containing resins are preferable, and water-repellentfluorine-containing resins excellent particularly in heat resistance andoxidation resistance are more preferable. Such resins include, forexample, sulfonated polytetrafluoroethylene, sulfonatedtetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, andsulfonated tetrafluoroethylene-hexafluoropropylene copolymers.

When the solid polymer electrolyte membrane is used in a fuel cell, aprocess for producing an assembly of the membrane and electrodes is notparticularly limited and a well-known process can be adopted. As aprocess for producing the membrane-electrodes assembly, there is, forexample, the following process. Pt catalyst powder supported on carbonis mixed with a polytetrafluoroethylene suspension, and the mixture isapplied on carbon paper and heat-treated to form a catalyst layer. Then,a solution of the same solid polymer electrolyte as that constitutingthe solid polymer electrolyte membrane is applied on the catalyst layer,and the thus treated catalyst layer and the solid polymer electrolytemembrane are united in a body by hot pressing.

In addition, there are, for example, a process of previously coating Ptcatalyst powder with a solution of the same solid polymer electrolyte asthat constituting the solid polymer electrolyte membrane, a process ofapplying a catalyst paste on the solid polymer electrolyte membrane, aprocess of conducting electroless plating on the solid polymerelectrolyte membrane to form electrodes, and a process of adsorbingcomplex ions of a metal of the platinum group on the solid polymerelectrolyte membrane and then reducing the same.

A solid polymer electrolyte fuel cell is constructed as follows. Apacking material (a supporting current collector) of thin carbon paperis adhered to each side of the assembly of the solid polymer electrolytemembrane and electrodes produced in the manner described above. Anelectroconductive separator (a bipolar plate) capable of serving as aseparator between electrode chambers and passageways for gas supply tothe electrodes is provided on the outer surface of each packing materialto obtain a single cell. A plurality of such single cells are laminated,with cooling plates or the like inserted between them, to obtain thesolid polymer electrolyte fuel cell. The fuel cell is preferablyoperated at a high temperature because the high-temperature operationenhances the catalytic activity of the electrodes and reduces theelectrode overvoltage. However, since the solid polymer electrolytemembrane does not function without water, the fuel cell has to beoperated at a temperature at which water control is possible. Apreferable range of the operating temperature for the fuel cell is arange of room temperature to 100° C.

DESCRIPTION OF PREFERRED EMBODIMENT

The present invention is illustrated in further detail with the examplesdescribed below. Conditions for measuring each physical property are asfollows.

(1) Ion-exchange Group Equivalent Weight

A certain amount (a: gram) of a polymer having sulfonic acid groupsintroduced thereinto through alkylene groups which was to be subjectedto measurement was accurately weighed into a closable glass container,and an excess amount of an aqueous calcium chloride solution was addedthereto and stirred overnight. Hydrogen chloride produced in the systemwas titrated (b: ml) with a 0.1N aqueous sodium hydroxide standardsolution (f: titer) by using phenolphthalein as an indicator. Theion-exchange group equivalent weight (g/equivalent) was calculated bythe following equation:

 Ion-exchange group equivalent weight=(1000×a)/(0.1×b×f)  [Expression 1]

(2) Evaluation of the Output Capability of a Single Cell for Fuel Cell

An assembly of a solid polymer electrolyte membrane and electrodes wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated.

Hydrogen and oxygen were used as reactive gases. Each of them was wettedby passage through a water bubbler at 23° C. at a pressure of 1atmosphere and then supplied to the cell for evaluation. The gas flowrates were as follows: hydrogen 60 ml/min and oxygen 40 ml/min. The celltemperature was 70° C. The output capability of the fuel cell wasevaluated with a H201B charge and discharge apparatus (mfd. by HokutoDenko Co., Ltd.).

EXAMPLE 1

(1) Synthesis of a sulfopropylated poly(1,4-biphenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 6.00 g(0.0155 mol) of a poly(1,4-biphenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-C₆H₄-4-O—)_(n)] dried by its maintenance at110° C. for 10 hours and 150 ml of dehydrated chloroform for synthesiswere placed in the flask and maintained at 60° C. for about 1 hour toeffect dissolution. To the resulting solution was added 2.83 g (0.0232mol) of propanesultone.

Subsequently, 3.10 g (0.0232 mol) of anhydrous aluminum chloride wasadded thereto with stirring over a period of about 30 minutes. Aftercompletion of the addition of anhydrous aluminum chloride, the resultingmixture was stirred with heating at 50° C. for 15 hours. The precipitatewas filtered, washed with 150 ml of chloroform and then dried underreduced pressure. The dried precipitate was suspended in 250 ml ofwater, finely ground in a mixer and then filtered. This procedure wasrepeated four times, followed by thorough washing with water, and thewater-insoluble finely ground substance thus obtained was dried at 90°C. under reduced pressure.

The dried substance was subjected to ¹H-NMR to find that new peaks dueto a —CH₂CH₂CH₂SO₃H group were present at 2.2 ppm and 3.8 ppm. This factconfirmed the introduction of sulfopropyl groups. The sulfonic acidequivalent weight of the sulfopropylated poly(1,4-biphenylene etherether sulfone) solid polymer electrolyte I thus obtained was 1,100g/equivalent.

Since the sulfopropylated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte I can be produced through one step by usingthe poly(1,4-biphenylene ether ether sulfone), a relatively inexpensivecommercial engineering plastic, as a starting material, the cost ofproduction thereof is as low as less than one-fiftieth that of aperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

The sulfopropylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte I is advantageous from the viewpoint of cost becauseit can be produced through one step and hence can be synthesized at alower cost as compared with a sulfomethylated poly(1,4-biphenylene etherether sulfone) solid polymer electrolyte VII and a sulfohexamethylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte VIIIwhich are produced through two steps as described hereinafter inExamples 11 and 12.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfopropylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte I and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte Iwas measured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfopropylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte I was 1,100 g/equivalent, the same value as theinitial value, namely, the solid polymer electrolyte I was stable likethe expensive perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117).

On the other hand, as described hereinafter in Comparative Example 1,(1), the ion-exchange group equivalent weight of an inexpensivesulfonated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte II was increased to 1,200 g/equivalent from its initialvalue of 650 g/equivalent under the same conditions of hydrolysis byheating as above, namely, sulfonic acid groups were released from thesolid polymer electrolyte II.

Thus, unlike the inexpensive sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte II described hereinafter inComparative Example 1, (1), the inexpensive sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte Iwas stable like the expensive perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117) and was excellent in both cost andresistance to hydrolysis (durability).

(2) Formation of a Solid Polymer Electrolyte Membrane

The solid polymer electrolyte I obtained in the above item (1) wasdissolved in a N,N-dimethylformamide-cyclohexanone-methyl ethyl ketonemixed solvent (volume ratio; 20:80:25) to a concentration of 5 wt %. Theresulting solution was spread on a glass plate by spin coating,air-dried and then dried in vacuo at 80° C. to form a solid polymerelectrolyte membrane I of 25 μm in thickness. The ion electricconductivity of the obtained solid polymer electrolyte membrane I was 1S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane I and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, the ionelectric conductivity of the solid polymer electrolyte membrane I wasthe same as its initial value like that of a perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117) produced at a highcost, and the solid polymer electrolyte membrane I was firm.

On the other hand, as described hereinafter in Comparative Example 1,(2), a relatively inexpensive sulfonated poly(1,4-biphenylene etherether sulfone) solid polymer electrolyte membrane II was broken totatters under the same conditions of hydrolysis by heating as above.

Thus, unlike the sulfonated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte membrane II described hereinafter inComparative Example 1, the inexpensive sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane I was stable like the expensive perfluorocarbon sulfonic acidsolid polymer electrolyte membrane (Nafion 117) and was excellent inboth cost and resistance to hydrolysis (durability).

(3) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte I in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution I).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution I and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution I after the maintenance was measured. As a result, it was foundthat the ion-exchange group equivalent weight of said solution I was1,100 g/equivalent, the same value as the initial value, namely, thesolution I was stable like an expensive perfluorocarbon sulfonic acid(Nafion 117) electrocatalyst-coating solution.

On the other hand, as described hereinafter in Comparative Example 1,(2), the ion-exchange group equivalent weight of anelectrocatalyst-coating solution II was increased to 1,200 g/equivalentfrom its initial value of 650 g/equivalent under the same conditions ofhydrolysis by heating as above, namely, sulfonic acid groups werereleased.

Thus, unlike the inexpensive electrocatalyst-coating solution IIdescribed hereinafter in Comparative Example 1, (2), the inexpensiveelectrocatalyst-coating solution I was stable like the expensiveperfluorocarbon sulfonic acid (Nafion 117) electrocatalyst-coatingsolution and was excellent in both cost and resistance to hydrolysis(durability).

The aforesaid electrocatalyst-coating solution I was applied on bothsides of the solid polymer electrolyte membrane I obtained in the aboveitem (2), and was dried to produce a membrane-electrodes assembly Ihaving an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution II described hereinafter inComparative Example 1, (2) was applied on both sides of the same solidpolymer electrolyte membrane I as that obtained in the above item (2),and was dried to produce a membrane-electrodes assembly I′ having anamount of platinum supported of 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte (Nafion 117) in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane I as that obtainedin the above item (2), and was dried to produce a membrane-electrodesassembly I″ having an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly I obtained and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. The membrane-electrodes assemblyI after the maintenance was not different from that before themaintenance like a membrane-electrodes assembly produced at a high costby using the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and the perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly I′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly I′ after the maintenance, the electrodes were peeling a littlebut the membrane was firm. The assembly I′ after the maintenance hadpower-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly I″ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly I″ after the maintenance, the electrodes were peeling a littlebut the membrane was firm. The assembly I″ after the maintenance hadpower-generating capability.

On the other hand, as described hereinafter in Comparative Example 1,(3), the membrane of a membrane-electrodes assembly II produced by usingthe sulfonated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte membrane II and the electrocatalyst-coating solution II wasbroken to tatters and its electrodes were peeled, under the sameconditions of hydrolysis by heating as above.

Thus, unlike the membrane-electrodes assembly II described hereinafterin Comparative Example 1, (3), i.e., the assembly of the sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane and electrodes, the inexpensive assembly of the sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane and electrodes was stable like the expensive assembly of theperfluorocarbon sulfonic acid (Nafion 117) membrane and electrodes, andcould be obtained as an assembly excellent in both cost and resistanceto hydrolysis (durability).

(4) Durability Test on Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies I, I′ and I″ wereallowed to absorb water by immersion in boiling deionized water for 2hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated. In detail, the singlecell for solid polymer electrolyte fuel cell shown in FIG. 1 wasproduced by adhering a packing material (a supporting current collector)5 of thin carbon paper to each of the electrodes of eachmembrane-electrodes assembly 4 obtained in Example 1 and composed of asolid polymer electrolyte membrane 1, an oxygen electrode 2 and ahydrogen electrode 3, and providing an electroconductive separator (abipolar plate) 6 capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material.

The single cells for solid polymer electrolyte fuel cell thus obtainedwere subjected to a long-term operation test at a current density of 300mA/cm². The results obtained are shown in FIG. 2.

In FIG. 2, numerals 12, 13 and 14 indicate the results of the durabilitytest on the single cells for fuel cell obtained by the use of themembrane-electrodes assemblies I, I′ and I″, respectively. In FIG. 2,numeral 15 indicates the result of the durability test on a single cellfor fuel cell obtained by using the assembly of the perfluorocarbonsulfonic acid (Nafion 117) membrane and electrodes.

In FIG. 2, numeral 12 indicates the change with time of output voltageof the single cell for fuel cell of Example 1 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 13 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 1 byusing a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

Numeral 14 indicates the change with time of output voltage of thesingle cell for fuel produced in Example 1 by using a solid polymerelectrolyte membrane of the polyether ether sulfone having sulfonic acidgroups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the perfluorocarbon sulfonicacid solid polymer electrolyte (Nafion 117). Numeral 15 indicates thechange with time of output voltage of the single cell for fuel cellobtained by using the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117). Numeral 16 indicates the change withtime of output voltage of the single cell for fuel cell of ComparativeExample 1 produced by using a solid polymer electrolyte membrane of apolyether ether sulfone having sulfonic acid groups directly bondedthereto and an electrocatalyst-coating solution containing the polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

As indicated by numerals 12 and 14 in FIG. 2, the initial output voltageof each of the single cells for fuel cell obtained by using themembrane-electrodes assemblies I and I″, respectively, is 0.70 V whichis lower than the output voltage of the single cell for fuel cellindicated by numeral 15 in FIG. 2, i.e., the single cell for fuel cellproduced by using the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117). However, since the output voltage ofeach of the single cells using the membrane-electrodes assemblies I andI″, respectively, is the same as its initial value even after 5,000hours of operation, these single cells can be satisfactorily used in afuel cell formed by laminating single cells of each kind, when thenumber of the single cells laminated is increased.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 16 in FIG. 2 (the single cell for fuelcell obtained by using the sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte II which is described hereinafter inComparative Example 1) was 0.73 V, and the output of this single cellwas zero after 600 hours of operation. From this fact, it is clear thatthe single cell for fuel cell produced by using the solid polymerelectrolyte membrane I of the sulfopropylated poly(1,4-biphenylene etherether sulfone) obtained by bonding sulfonic acid groups to the aromaticrings of a poly(1,4-biphenylene ether ether sulfone) is superior indurability to the single cell for fuel cell produced by using the solidpolymer electrolyte membrane II of a poly(1,4-biphenylene ether ethersulfone) having sulfonic acid groups directly bonded thereto.

As can be seen from FIG. 2, the single cells for fuel cell obtained byusing the membrane-electrodes assemblies I and I″, respectively, aresuperior in durability to the single cell for fuel cell obtained byusing the membrane-electrodes assembly I′. That is, theelectrocatalyst-coating solution I is more suitable than theelectrocatalyst-coating solution II, for coating an electrocatalyst fora membrane-electrodes assembly.

(5) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (4)according to the present invention. The fuel cell had an output of 3 kW.

Comparative Example 1

(1) Synthesis of a sulfonated poly(1,4-biphenylene ether ether sulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 4.00 g(0.0103 mol) of a poly(1,4-biphenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-C₆H₄-4-O—)_(n)] dried by its maintenance at110° C. for 10 hours and 100 ml of dehydrated chloroform were placed inthe flask and maintained at 60° C. for about 1 hour to effectdissolution. To the resulting solution was added 50 ml of a solution of1.165 g (0.01 mol) of chlorosulfonic acid in 1,1,2,2-tetrachloroethaneover a period of about 10 minutes.

Subsequently, the resulting mixture was stirred at 60° C. for 4 hours.The precipitate was filtered and then washed with 150 ml of chloroform.The washed precipitate was dissolved in 250 ml of methanol at 60° C.,and the resulting solution was dried at 60° C. under reduced pressure.

The polymer thus obtained was finely ground together with 250 ml ofwater in a mixer, and the resulting mixture was filtered. This procedurewas repeated three times and the water-insoluble fine powder thusobtained was dried over phosphorus pentaoxide at 90° C. under reducedpressure.

This fine powder was insoluble in water and soluble in methanol. Thedried fine powder was subjected to ¹HNMR measurement to find thatabsorptions at 7.3 to 8.00 ppm due to the hydrogen atoms of the phenylgroups in the starting poly(1,4-biphenylene ether ether sulfone) hadbeen decreased, and that a new absorption due to the hydrogen atom of aphenyl group adjacent to a SO₃H group was present at 8.3 ppm. This factconfirmed the introduction of sulfonic acid groups. The sulfonic acidequivalent weight of the sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte II thus obtained was 650g/equivalent.

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidsulfonated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte II and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte IIwas measured.

As a result, it was found that the sulfonic acid equivalent weight ofthe sulfonated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte II had been increased to 1,200 g/equivalent from its initialvalue of 650 g/equivalent, namely, sulfonic acid groups had beenreleased.

(2) Formation of a Solid Polymer Electrolyte Membrane

The sulfonated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte II obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membrane IIof 45 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane II was 3 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane II and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. As a result, the obtained solidpolymer electrolyte membrane II was broken to tatters.

(3) Production of an Electrocatalyst-coating Solution and aMembrane-electrodes Assembly

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte II in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution II).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution II and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution II after the maintenance was measured. As a result, it wasfound that the ion-exchange group equivalent weight of theelectrocatalyst-coating solution II had been increased to 1,200g/equivalent from its initial value of 650 g/equivalent, namely,sulfonic acid groups had been released.

The aforesaid electrocatalyst-coating solution II was applied on bothsides of the solid polymer electrolyte membrane II obtained in the aboveitem (2), and was dried to produce a membrane-electrodes assembly IIhaving an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly II obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. As a result, the membraneof the membrane-electrodes assembly II was broken to tatters and itselectrodes were peeled.

(4) Durability Test on a Single Cell for Fuel Cell

A single cell for solid polymer electrolyte fuel cell was produced byadhering a packing material (a supporting current collector) of thincarbon paper to each side of the membrane-electrodes assembly IIobtained in Comparative Example 1, and providing an electroconductiveseparator (a bipolar plate) capable of serving as a separator betweenelectrode chambers and passageways for gas supply to the electrodes, onthe outer surface of each packing material. The single cell wassubjected to a long-term operation test at a current density of 300mA/cm².

As a result, it was found that as indicated by numeral 16 in FIG. 2, theinitial output voltage of the single cell was 0.73 V and that the outputvoltage of the single cell was zero after 600 hours of operation.

EXAMPLE 2

(1) Synthesis of a sulfopropylated poly(1,4-biphenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 22.6 g(0.0155 mol) of a poly(1,4-biphenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-C₆H₄-4-O—)_(n)] dried by its maintenance at110° C. for 10 hours and 150 ml of dehydrated 1,1,2-trichloroethane wereplaced in the flask and maintained at 113° C. for about 1 hour to effectdissolution. To the resulting solution was added 24.8 g (0.0155 mol) ofpropanesultone.

Subsequently, 6.19 g (0.0464 mol) of anhydrous aluminum chloride wasadded thereto with stirring over a period of about 30 minutes. Aftercompletion of the addition of anhydrous aluminum chloride, the resultingmixture was stirred at 113° C. for 30 hours. The polymer precipitatedwas filtered, washed with 150 ml of chloroform and then dried underreduced pressure. The dried polymer was suspended in 250 ml of water andfinely ground in a mixer, and the resulting finely ground substance wasfiltered. This procedure was repeated four times.

After thorough washing with water, the water-insoluble finely groundsubstance thus obtained was dried at 90° C. under reduced pressure. Thedried substance was subjected to ¹HNMR measurement to find that newpeaks due to a —CH₂CH₂CH₂SO₃H group were present at 2.2 ppm and 3.8 ppm.This fact confirmed the introduction of sulfopropyl groups. The sulfonicacid equivalent weight of the sulfopropylated poly(1,4-biphenylene etherether sulfone) solid polymer electrolyte III thus obtained was 430g/equivalent.

Since the sulfopropylated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte III can be produced through one step by usingthe poly(1,4-biphenylene ether ether sulfone), a relatively inexpensivecommercial engineering plastic, as a starting material, the cost ofproduction thereof is as low as less than one-fiftieth that of theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfopropylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte III and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte IIIwas measured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfopropylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte III was 430 g/equivalent, the same value as theinitial value, namely, the solid polymer electrolyte III was stable likethe expensive perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117).

On the other hand, as described in Comparative Example 1, (1), theion-exchange group equivalent weight of the sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte IIwas increased to 1,200 g/equivalent from its initial value of 650g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released from the solid polymerelectrolyte II.

Thus, unlike the sulfonated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte II described in Comparative Example 1, (1),the inexpensive sulfopropylated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte III was stable like the expensiveperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117) andwas excellent in both cost and resistance to hydrolysis (durability).

(2) Formation of a Solid Polymer Electrolyte Membrane

The product obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membraneIII of 25 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane III was 55 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane III and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, the ionelectric conductivity of the solid polymer electrolyte membrane III wasthe same as its initial value like that of the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117) produced at a highcost, and the solid polymer electrolyte membrane III was firm.

On the other hand, as described in Comparative Example 1, (2), thesulfonated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte membrane II was broken to tatters under the same conditionsof hydrolysis by heating as above.

Thus, unlike the inexpensive sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane II described in ComparativeExample 1, (2), the inexpensive sulfopropylated poly(1,4-biphenyleneether ether sulfone) solid polymer electrolyte membrane III was stablelike the expensive perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117) and was excellent in both cost andresistance to hydrolysis (durability).

(3) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte III in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution III).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution III and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution III after the maintenance was measured.

As a result, it was found that the ion-exchange group equivalent weightof the electrocatalyst-coating solution III was 430 g/equivalent, thesame value as the initial value, namely, the electrocatalyst-coatingsolution III was stable like the expensive perfluorocarbon sulfonic acid(Nafion 117) electrocatalyst-coating solution.

On the other hand, as described in Comparative Example 1, (2), theion-exchange group equivalent weight of the electrocatalyst-coatingsolution II was increased to 1,200 g/equivalent from its initial valueof 650 g/equivalent under the same conditions of hydrolysis by heatingas above, namely, sulfonic acid groups were released. Thus, unlike theinexpensive electrocatalyst-coating solution II described in ComparativeExample 1, (2), the inexpensive electrocatalyst-coating solution III wasstable like the expensive perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution and was excellent in both cost andresistance to hydrolysis (durability).

The aforesaid electrocatalyst-coating solution III was applied on bothsides of the solid polymer electrolyte membrane III obtained in theabove item (2), and was dried to produce a membrane-electrodes assemblyIII having an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution II described in Comparative Example1, (2) was applied on both sides of the same solid polymer electrolytemembrane III as that obtained in the above item (2), and was dried toproduce a membrane-electrodes assembly III′ having an amount of platinumsupported of 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution).

This electrocatalyst-coating solution was applied on both sides of thesame solid polymer electrolyte membrane III as that obtained in theabove item (2), and was dried to produce a membrane-electrodes assemblyIII″ having an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly III obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly III was not different from that before themaintenance like a membrane-electrodes assembly produced at a high costby using the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and the perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly III′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly III′ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly III′ after themaintenance had a power-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly III″ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly III″ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly III″ after themaintenance had power-generating capability.

On the other hand, as described in Comparative Example 1, (3), themembrane of the membrane-electrodes assembly II produced by using therelatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane II and the electrocatalyst-coating solution II wasbroken to tatters and its electrodes were peeled, under the sameconditions of hydrolysis by heating as above. Thus, unlike theinexpensive membrane-electrodes assembly II described in ComparativeExample 1, (3), i.e., the assembly of the sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane and electrodes, the inexpensive assembly of the sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane and electrodes was stable like the expensive assembly of theperfluorocarbon sulfonic acid (Nafion 117) membrane and electrodes, andwas excellent in both cost and resistance to hydrolysis (durability).

(4) Evaluation of the Output Capability of Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies III, III′ and III″were allowed to absorb water by immersion in boiling deionized water for2 hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated.

In detail, the single cell for solid polymer electrolyte fuel cell shownin FIG. 1 was produced by adhering a packing material (a supportingcurrent collector) 5 of thin carbon paper to each of the electrodes ofeach membrane-electrodes assembly 4 obtained in Example 2 and composedof a solid polymer electrolyte membrane 1, an oxygen electrode 2 and ahydrogen electrode 3, and providing an electroconductive separator (abipolar plate) 6 capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material. The single cells for solid polymerelectrolyte fuel cell thus obtained were subjected to a long-termoperation test at a current density of 300 mA/cm². The results obtainedare shown in FIG. 3. In FIG. 3, numerals 17, 18 and 19 indicate theresults of the durability test on the single cells using themembrane-electrodes assemblies III, III′ and III″, respectively.

In FIG. 3, numeral 17 indicates the change with time of output voltageof the single cell for fuel cell of Example 2 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 18 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 2 byusing a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

Numeral 19 indicates the change with time of output voltage of thesingle cell for fuel cell produced in Example 2 by using a solid polymerelectrolyte membrane of the polyether ether sulfone having sulfonic acidgroups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the perfluorocarbon sulfonicacid solid polymer electrolyte (Nafion 117). Numeral 20 indicates thechange with time of output voltage of a single cell for fuel cellobtained by using the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117). Numeral 21 indicates the change withtime of output voltage of a single cell for fuel cell of ComparativeExample 2 produced by using a solid polymer electrolyte membrane of apolyether ether sulfone having sulfonic acid groups directly bondedthereto and an electrocatalyst-coating solution containing the polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

In FIG. 3, numeral 20 indicates the result of the durability test on thesingle cell for fuel cell obtained by using the assembly of theperfluorocarbon sulfonic acid (Nafion 117) membrane and electrodes.

As indicated by numerals 17 and 19 in FIG. 3, the initial output voltageof each of the single cells for fuel cell obtained by using themembrane-electrodes assemblies III and III″, respectively, is 0.88 V,and the output voltage of each single cell is decreased to about 94% ofthe initial output voltage after 5,000 hours of operation. The decreasedvalue, however, is substantially the same as the output voltage of thesingle cell for fuel cell produced by using the assembly of theperfluorocarbon sulfonic acid (Nafion 117) membrane and electrodes.Therefore, each of the single cells obtained by using themembrane-electrodes assemblies III and III″, respectively, can besatisfactorily used in a fuel cell.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 21 in FIG. 3 (the single cell for fuelcell of Comparative Example 2 obtained by using the sulfonated aromatichydrocarbon solid polymer electrolyte II) was 0.73 V, and the outputvoltage of this single cell was zero after 600 hours of operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte III obtainedby bonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte II having sulfonic acid group directly bondedthereto.

The single cells for fuel cell obtained by using the membrane-electrodesassemblies III and III″, respectively, are superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly III′.

That is, the electrocatalyst-coating solution III is more suitable forcoating an electrocatalyst for a membrane-electrodes assembly than theelectrocatalyst-coating solution II described in Comparative Example 1.The reason why the output voltage of the single cell for fuel cell ofExample 2 is higher than that of the single cell for fuel cell ofComparative Example 2 though the membrane-electrodes assemblies ofExample 2 and Comparative Example 2 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane III and electrocatalyst-coatingsolution III used in the membrane-electrodes assembly III of Example 2is higher than that of the solid polymer electrolyte membrane II andelectrocatalyst-coating solution II used in the membrane-electrodesassembly II of Comparative Example 2.

(5) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (4)according to the present invention. The fuel cell had an output of 3 kW.

EXAMPLE 3

(1) Synthesis of a sulfopropylated poly(1,4-biphenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 6.00 g(0.0155 mol) of a dried poly(1,4-biphenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-C₆H₄-4-O—)_(n)] and 150 ml of dehydratedchloroform for synthesis were placed in the flask and maintained at 60°C. for about 1 hour to effect dissolution. To the resulting solution wasadded 5.67 g (0.0464 mol) of propanesultone.

Subsequently, 6.19 g (0.0464 mol) of anhydrous aluminum chloride wasadded thereto with stirring over a period of about 30 minutes. Aftercompletion of the addition of anhydrous aluminum chloride, the resultingmixture was refluxed with stirring at 60° C. for 30 hours. Theprecipitate was filtered, washed with 150 ml of chloroform and thendried under reduced pressure. The dried precipitate was suspended in 250ml of water, finely ground in a mixer, and then filtered. This procedurewas repeated four times.

After thorough washing with water, the water-insoluble finely groundsubstance thus obtained was dried at 90° C. under reduced pressure. Thedried substance was subjected to ¹HNMR measurement to find that newpeaks due to a —CH₂CH₂CH₂SO₃H group were present at 2.2 ppm and 3.8 ppm.

This fact confirmed the introduction of sulfopropyl groups. The sulfonicacid equivalent weight of the sulfopropylated poly(1,4-biphenylene etherether sulfone) solid polymer electrolyte IV thus obtained was 970g/equivalent.

Since the sulfopropylated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte IV can be produced through one step by usingthe poly(1,4-biphenylene ether ether sulfone), a relatively inexpensivecommercial engineering plastic, as a starting material, the cost ofproduction thereof is as low as less than one-fiftieth that of theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfopropylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte IV and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte IVwas measured.

The ion-exchange group equivalent weight of the solid polymerelectrolyte IV was 970 g/equivalent, the same value as the initialvalue, namely, the solid polymer electrolyte IV was stable like theexpensive perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117).

On the other hand, the ion-exchange group equivalent weight of theinexpensive sulfonated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte II of Comparative Example 1 was increased to 1,200g/equivalent from its initial value of 650 g/equivalent under the sameconditions of hydrolysis by heating as above, namely, sulfonic acidgroups were released from the solid polymer electrolyte II. Thus, unlikethe sulfonated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte II of Comparative Example 1, the inexpensive sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte IVwas stable like the perfluorocarbon sulfonic acid solid polymerelectrolyte (Nafion 117) and was excellent in both cost and resistanceto hydrolysis (durability).

(2) Formation of a Solid Polymer Electrolyte Membrane

The solid polymer electrolyte IV obtained in the above item (1) wasdissolved in a N,N-dimethylformamide-cyclohexanone-methyl ethyl ketonemixed solvent (volume ratio; 20:80:25) to a concentration of 5 wt %. Theresulting solution was spread on a glass plate by spin coating,air-dried and then dried in vacuo at 80° C. to form a solid polymerelectrolyte membrane IV of 25 μm in thickness. The ion electricconductivity of the electrolyte membrane IV was 10 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane IV and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, the ionelectric conductivity of the solid polymer electrolyte membrane IV wasthe same as its initial value like that of the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117) produced at a highcost, and the solid polymer electrolyte membrane IV was firm.

On the other hand, as described in Comparative Example 1, (2), therelatively inexpensive sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane II was broken to tattersunder the same conditions of hydrolysis by heating as above.

Thus, unlike the sulfonated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte membrane II, the inexpensive sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane IV was stable like the perfluorocarbon sulfonic acid solidpolymer electrolyte membrane (Nafion 117) and was excellent in both costand resistance to hydrolysis (durability).

(3) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte IV in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution IV).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution IV and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution IV after the maintenance was measured.

As a result, it was found that the ion-exchange group equivalent weightof the electrocatalyst-coating solution IV was 970 g/equivalent, thesame value as the initial value, namely, the electrocatalyst-coatingsolution IV was stable like the perfluorocarbon sulfonic acid (Nafion117) electrocatalyst-coating solution.

On the other hand, the ion-exchange group equivalent weight of theelectrocatalyst-coating solution II of Comparative Example 1 wasincreased to 1,200 g/equivalent from its initial value of 650g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released.

Thus, unlike the electrocatalyst-coating solution II of ComparativeExample 1, the inexpensive electrocatalyst-coating solution IV wasstable like the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution and was excellent in both cost andresistance to hydrolysis (durability).

The aforesaid electrocatalyst-coating solution IV was applied on bothsides of the solid polymer electrolyte membrane IV obtained in the aboveitem (2), and was dried to produce a membrane-electrodes assembly IVhaving an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution II of Comparative Example 1 wasapplied on both sides of the same solid polymer electrolyte membrane IVas that obtained in the above item (2), and was dried to produce amembrane-electrodes assembly IV′ having an amount of platinum supportedof 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte (Nafion 117) in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane IV as that obtainedin the above item (2), and was dried to produce a membrane-electrodesassembly IV″ having an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly IV obtained and 20 ml of ion-exchangedwater were maintained at 12⁰° C. for 2 weeks. The membrane-electrodesassembly IV after the maintenance was not different from that before themaintenance like a membrane-electrodes assembly produced at a high costby using the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and the perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly IV′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly IV′ after the maintenance, the electrodes were peeling a littlebut the membrane was firm. The assembly IV′ after the maintenance hadpower-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly IV″ and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. In the membrane-electrodes assemblyIV″ after the maintenance, the electrodes were peeling a little but themembrane was firm. The assembly IV″ after the maintenance hadpower-generating capability.

On the other hand, as described in Comparative Example 1, (3), themembrane of the membrane-electrodes assembly II produced by using therelatively inexpensive sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane II and theelectrocatalyst-coating solution II was broken to tatters and itselectrodes were peeled, under the same conditions of hydrolysis byheating as above.

Thus, unlike the inexpensive membrane-electrodes assembly II ofComparative Example 1, i.e., the assembly of the sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane and electrodes, the inexpensive assembly of the sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane and electrodes was stable like the assembly of theperfluorocarbon sulfonic acid (Nafion 117) membrane and electrodes, andwas excellent in both cost and resistance to hydrolysis (durability).

(4) Durability Test on Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies IV, IV′ and IV″ wereallowed to absorb water by immersion in boiling deionized water for 2hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated. In detail, the singlecell for solid polymer electrolyte fuel cell shown in FIG. 1 wasproduced by adhering a packing material (a supporting current collector)5 of thin carbon paper to each of the electrodes of eachmembrane-electrodes assembly 4 obtained in Example 3 and composed of asolid polymer electrolyte membrane 1, an oxygen electrode 2 and ahydrogen electrode 3, and providing an electroconductive separator (abipolar plate) 6 capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material.

The single cells for solid polymer electrolyte fuel cell thus obtainedwere subjected to a long-term operation test at a current density of 300mA/cm². In FIG. 4, numerals 22, 23 and 24 indicate the results of thedurability test on the single cells for fuel cell obtained by using themembrane-electrodes assemblies IV, IV′ and IV″, respectively. In FIG. 4,numeral 25 indicates the result of the durability test on a single cellfor fuel cell obtained by using the assembly of the perfluorocarbonsulfonic acid (Nafion 117) membrane and electrodes.

In FIG. 4, numeral 22 indicates the change with time of output voltageof the single cell for fuel cell of Example 3 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 23 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 3 byusing a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

Numeral 24 indicates the change with time of output voltage of thesingle cell for fuel cell produced in Example 3 by using a solid polymerelectrolyte membrane of the polyether ether sulfone having sulfonic acidgroups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the perfluorocarbon sulfonicacid solid polymer electrolyte (Nafion 117). Numeral 25 indicates thechange with time of output voltage of the single cell for fuel cellobtained by using the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117). Numeral 26 indicates the change withtime of output voltage of a single cell for fuel cell of ComparativeExample 3 produced by using a solid polymer electrolyte membrane of apolyether ether sulfone having sulfonic acid groups directly bondedthereto and an electrocatalyst-coating solution containing the polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

In the case of numerals 22 and 24 in FIG. 4, the initial output voltagewas 0.78 V, and the output voltage had the same value as its initialvalue even after 5,000 hours of operation. These results were equal tothose obtained by the use of the perfluorocarbon sulfonic acid solidpolymer electrolyte membrane (Nafion 117) IV and indicated by numeral 25in FIG. 4.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 26 in FIG. 4 (the single cell for fuelcell of Comparative Example 1 obtained by using the sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte II)was 0.73 V, and the output of this single cell was zero after 600 hoursof operation.

From this fact, it is clear that the single cell for fuel cell producedby using the solid polymer electrolyte membrane IV of apoly(1,4-biphenylene ether ether sulfone) having sulfonic acid groupsbonded to its aromatic rings through alkylene groups is superior indurability to the single cell for fuel cell produced by using the solidpolymer electrolyte membrane II of a poly(1,4-biphenylene ether ethersulfone) having sulfonic acid groups directly bonded thereto.

The single cells for fuel cell obtained by using the membrane-electrodesassemblies IV and IV″, respectively, are superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly IV′. That is, the electrocatalyst-coating solution IV is moresuitable for coating an electrocatalyst for a membrane-electrodesassembly than the electrocatalyst-coating solution II of ComparativeExample 1.

The reason why the output voltage of the single cell for fuel cell ofExample 3 is higher than that of the single cell for fuel cell ofComparative Example 1 though the membrane-electrodes assemblies ofExample 3 and Comparative Example 1 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane IV and electrocatalyst-coatingsolution IV used in the membrane-electrodes assembly of Example 3 ishigher than that of the solid polymer electrolyte membrane II andelectrocatalyst-coating solution II used in the membrane-electrodesassembly of Comparative Example 1.

(5) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (4)according to the present invention. The fuel cell had an output of 3 kW.

EXAMPLE 4

(1) Synthesis of a sulfopropylated poly(1,4-biphenylene ether ethersulfone)

In an autoclave, 6.00 g (0.0155 mol) of a dried poly(1,4-biphenyleneether ether sulfone) [(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-C₆H₄-4-O—)_(n)] and 150ml of dehydrated chloroform were maintained at 60° C. for about 1 hourto effect dissolution. To the resulting solution was added 5.67 g(0.0464 mol) of propanesultone.

Subsequently, 6.19 g (0.0464 mol) of anhydrous aluminum chloride wasadded thereto with stirring over a period of about 30 minutes. Aftercompletion of the addition of anhydrous aluminum chloride, the resultingmixture was stirred at 130° C. for 20 hours. The polymer precipitatedwas filtered, washed with 150 ml of chloroform and then dried underreduced pressure. The dried polymer was suspended in 250 ml of water andfinely ground in a mixer, and the resulting finely ground substance wasfiltered. This procedure was repeated four times.

After thorough washing with water, the water-insoluble finely groundsubstance thus obtained was dried at 90° C. under reduced pressure. Thedried substance was subjected to ¹HNMR measurement to find that newpeaks due to a —CH₂CH₂CH₂SO₃H group were present at 2.2 ppm and 3.8 ppm.This fact confirmed the introduction of sulfopropyl groups. The sulfonicacid equivalent weight of the sulfopropylated poly(1,4-biphenylene etherether sulfone) solid polymer electrolyte V thus obtained was 530g/equivalent.

Since the sulfopropylated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte V can be produced through one step by usingthe poly(1,4-biphenylene ether ether sulfone), a relatively inexpensivecommercial engineering plastic, as a starting material, the cost ofproduction thereof is as low as less than one-fiftieth that of theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfopropylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte V and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte Vwas measured. As a result, it was found that the ion-exchange groupequivalent weight of the solid polymer electrolyte V was 530g/equivalent, the same value as the initial value, namely, the solidpolymer electrolyte V was stable like the perfluorocarbon sulfonic acidsolid polymer electrolyte (Nafion 117).

On the other hand, as described in Comparative Example 1, (1), theion-exchange group equivalent weight of the inexpensive sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte IIwas increased to 1,200 g/equivalent from its initial value of 650g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released from the solid polymerelectrolyte II.

Thus, unlike the sulfonated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte II of Comparative Example 1, the inexpensivesulfopropylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte V was stable like the perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117) and was excellent in both cost andresistance to hydrolysis (durability).

(2) Formation of a Solid Polymer Electrolyte Membrane

The product obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membrane Vof 25 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane V was 20 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane V and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, the ionelectric conductivity of the solid polymer electrolyte membrane V wasthe same as its initial value like that of the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117) produced at a highcost, and the solid polymer electrolyte membrane V was firm.

On the other hand, as described in Comparative Example 1, (2), therelatively inexpensive sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane II was broken to tattersunder the same conditions of hydrolysis by heating as above. Thus,unlike the sulfonated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte membrane II of Comparative Example 1, theinexpensive sulfopropylated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte membrane V was stable like the perfluorocarbonsulfonic acid solid polymer electrolyte membrane (Nafion 117) and wasexcellent in both cost and resistance to hydrolysis (durability).

(3) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte V in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution V).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution V and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution V after the maintenance was measured. The ion-exchange groupequivalent weight of said solution V was 530 g/equivalent, the samevalue as the initial value, namely, said solution V was stable like theperfluorocarbon sulfonic acid (Nafion 117) electrocatalyst-coatingsolution.

On the other hand, as described in Comparative Example 1, (2), theion-exchange group equivalent weight of the electrocatalyst-coatingsolution II was increased to 1,200 g/equivalent from its initial valueof 650 g/equivalent under the same conditions of hydrolysis by heatingas above, namely, sulfonic acid groups were released. Thus, unlike theelectrocatalyst-coating solution II of Comparative Example 1, theinexpensive electrocatalyst-coating solution V was stable like theperfluorocarbon sulfonic acid (Nafion 117) electrocatalyst-coatingsolution and was excellent in both cost and resistance to hydrolysis(durability).

The aforesaid electrocatalyst-coating solution V was applied on bothsides of the solid polymer electrolyte membrane V obtained in the aboveitem (2), and was dried to produce a membrane-electrodes assembly Vhaving an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution II described in Comparative Example1, (2) was applied on both sides of the same solid polymer electrolytemembrane V as that obtained in the above item (2), and was dried toproduce a membrane-electrodes assembly V′ having an amount of platinumsupported of 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane V as that obtainedin the above item (2), and was dried to produce a membrane-electrodesassembly V″ having an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly V and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly V was not different from that before themaintenance like a membrane-electrodes assembly produced at a high costby using the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and the perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly V′ and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. In the membrane-electrodes assemblyV′ after the maintenance, the electrodes were peeling a little but themembrane was firm. The assembly V′ after the maintenance hadpower-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly V″ and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. In the membrane-electrodes assemblyV″ after the maintenance, the electrodes were peeling a little but themembrane was firm. The assembly V″ after the maintenance hadpower-generating capability.

On the other hand, as described in Comparative Example 1, (3), themembrane of the membrane-electrodes assembly II produced by using therelatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane II and the electrocatalyst-coating solution II wasbroken to tatters and its electrodes were peeled, under the sameconditions of hydrolysis by heating as above. Thus, unlike themembrane-electrodes assembly II of Comparative Example 1, i.e., theassembly of the sulfonated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte membrane and electrodes, the inexpensiveassembly of the sulfopropylated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane and electrodes was stablelike the assembly of the perfluorocarbon sulfonic acid (Nafion 117)membrane and electrodes, and was excellent in both cost and resistanceto hydrolysis (durability).

(4) Evaluation of the Output Capability of Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies V, V′ and V″ wereallowed to absorb water by immersion in boiling deionized water for 2hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated. FIG. 5 shows acurrent density-voltage plot obtained for the thus obtained single cellfor fuel cell incorporated with the membrane-electrodes assembly V.

The output voltage was 0.70 V at a current density of 1 A/cm² and 0.80 Vat a current density of 300 mA/cm². Thus, said single cell wassatisfactorily usable as a single cell for solid polymer electrolytefuel cell.

Then, a long-term operation test was carried out at a current density of300 mA/cm². The results obtained are shown in FIG. 6. In FIG. 6,numerals 27, 28 and 29 indicate the results of the durability test onthe single cells for fuel cell obtained by using the membrane-electrodesassemblies V, V′ and V″, respectively. In FIG. 6, numeral 30 indicatesthe result of the durability test on a single cell for fuel cellobtained by using the assembly of the perfluorocarbon sulfonic acid(Nafion 117) membrane and electrodes.

In FIG. 6, numeral 27 indicates the change with time of output voltageof the single cell for fuel cell of Example 4 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 28 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 4 byusing a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

Numeral 29 indicates the change with time of output voltage of thesingle cell for fuel cell produced in Example 4 by using a solid polymerelectrolyte membrane of the polyether ether sulfone having sulfonic acidgroups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the perfluorocarbon sulfonicacid solid polymer electrolyte (Nafion 117). Numeral 30 indicates thechange with time of output voltage of the single cell for fuel cellobtained by using the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117). Numeral 31 indicates the change withtime of output voltage of a single cell for fuel cell of ComparativeExample 4 produced by using a solid polymer electrolyte membrane of apolyether ether sulfone having sulfonic acid groups directly bondedthereto and an electrocatalyst-coating solution containing the polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

In the case of numerals 27 and 29 in FIG. 6, the initial output voltagewas 0.80 V, and the output voltage had substantially the same value asits initial value even after 5,000 hours of operation. These resultswere equal to those obtained by the use of the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117) and indicated bynumeral 30 in FIG. 6.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 31 in FIG. 6 (the single cell for fuelcell of Comparative Example 1 obtained by using the sulfonated aromatichydrocarbon solid polymer electrolyte II) was 0.73 V, and the output ofthis single cell was zero after 600 hours of operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte V obtainedby bonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte II having sulfonic acid groups directly bondedthereto.

The single cells for fuel cell obtained by using the membrane-electrodesassemblies V and V″, respectively, are superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly V′. That is, the electrocatalyst-coating solution V is moresuitable than the electrocatalyst-coating solution II, for coating anelectrocatalyst for a membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 4 is higher than that of the single cell for fuel cell ofComparative Example 1 though the membrane-electrodes assemblies ofExample 4 and Comparative Example 1 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane V and electrocatalyst-coatingsolution V used in the membrane-electrodes assembly V of Example 4 ishigher than that of the solid polymer electrolyte membrane II andelectrocatalyst-coating solution II used in the membrane-electrodesassembly II of Comparative Example 1.

As can be seen from Examples 3 and 4, the initial output voltage of asingle cell for fuel cell obtained by using a sulfoalkylated polyetherether sulfone solid electrolyte having a sulfonic acid equivalent weightof 530 to 970 g/equivalent is equal to or higher than the output voltageof a single cell for fuel cell obtained by using the perfluorocarbonsulfonic acid (Nafion 117) membrane. The former single cell for fuelcell is especially preferable because it is not deteriorated even whenoperated for 5,000 hours.

(5) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (4)according to the present invention. The fuel cell had an output of 3 kW.

EXAMPLES 5 TO 9

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 6.00 g(0.0155 mol) of a poly(1,4-biphenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-C₆H₄-4-O—)_(n)] dried by its maintenance at110° C. for 10 hours and 150 ml of a dehydrated solvent were placed inthe flask and heated to effect dissolution. To the resulting solutionwas added propanesultone.

Subsequently, anhydrous aluminum chloride thoroughly ground in a mortarwas added thereto with stirring over a period of about 30 minutes. Theproportions of propanesultone and anhydrous aluminum chloride are shownin Table 1.

After completion of the addition of anhydrous aluminum chloride, theresulting mixture was stirred at the temperature shown in Table 1 forthe time shown in Table 1.

The precipitate formed was filtered, washed with 150 ml of chloroformand then dried under reduced pressure. The dried precipitate wassuspended in 250 ml of water, finely ground in a mixer and thenfiltered. This procedure was repeated four times. After thorough washingwith water, the water-insoluble finely ground substance thus obtainedwas dried at 90° C. under reduced pressure. The dried substance wassubjected to ¹HNMR to find that new peaks due to a —CH₂CH₂CH₂SO₃H groupwere present at 2.2 ppm and 3.8 ppm. This fact confirmed theintroduction of sulfopropyl groups. There were carried out themeasurement of the sulfonic acid equivalent weight of the sulfoalkylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytesthus obtained and the evaluation of the resistance to deterioration bywater of the solid polymer electrolytes, solid polymer electrolytemembranes, electrocatalyst-coating solutions and assemblies of the solidpolymer electrolyte membrane and electrodes, and the evaluation ofsingle cells for fuel cell. The results obtained are shown in Table 1.

TABLE 1 Example Example Example Example Example 5 6 7 8 9 Propanesultone(g) 5.67 5.67 5.67 17.0 28.4 Anhydrous aluminum 6.20 6.20 6.20 18.6 24.8Dehydrated solvent 1,1,2- 1,1,2,2-tetra- 1,2,4- Chloro- Chloro-trichloro- chloro- trichloro- form form ethane ethane benzene Reactiontemp. (° C.) 113 145 150 60 60 Reaction time (hr) 12 12 12 15 12Ion-exchange group 620 610 590 730 680 equivalent weight (g/equivalent)Ion-exchange group 620 610 590 730 680 equivalent weight (g/equivalent)of a solid polymer electrolyte after its maintenance in ion- exchangedwater at 120° C. for 2 weeks Shape of a solid No No No No No polymerelectrolyte change change change change change membrane after itsmaintenance in ion- exchanged water at 120° C. for 2 weeks Ionicconductivity 16 17 19 13 15 (S/cm) of a solid polymer electrolytemembrane Ion-exchange group 620 610 590 730 680 equivalent weight(g/equivalent) of an electrocatalyst- coating solution containing asolid polymer electrolyte, after its maintenance in ion-exchanged waterat 120° C. for 2 weeks Shape of an assembly No No No No No of a solidpolymer change change change change change electrolyte membrane andelectrodes after its maintenance in ion-exchanged water at 120° C. for 2weeks Initial output (V) of 0.80 0.80 0.81 0.79 0.79 a single cell at300 mA/cm² Output (% based on 97 98 97 99 98 initial value) of a singlecell after 5,000 hours of operation at 300 mA/cm²

Since the sulfoalkylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolytes can be produced through one step by using aninexpensive commercial engineering plastic as a starting material, thecost of production thereof is as low as less than one-forties that ofthe perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

In a Teflon-coated closed container made of SUS, each of thesulfoalkylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolytes of Examples 5 to 9 was maintained at 120° C. for 2 weeks inion-exchanged water. The sulfonic acid equivalent weight of each solidpolymer electrolyte after the maintenance was the same as its initialvalue unlike that of the sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte II of Comparative Example 1, namely,the solid polymer electrolytes of Examples 5 to 9 were stable like theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117).Thus, the solid polymer electrolytes of Examples 5 to 9 were excellentin both cost and resistance to hydrolysis (durability).

In a Teflon-coated closed container made of SUS, each of thesulfoalkylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte membranes of Examples 5 to 9 was maintained at 120° C. for 2weeks in ion-exchanged water. The shape of each solid polymerelectrolyte membrane after the maintenance was the same as the initialshape unlike that of the sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane of Comparative Example 1,namely, the solid polymer electrolyte membranes of Examples 5 to 9 werestable like the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117). Thus, the solid polymer electrolyte membranes ofExamples 5 to 9 were excellent in both cost and resistance to hydrolysis(durability).

In a Teflon-coated closed container made of SUS, each of theelectrocatalyst-coating solutions of Examples 5 to 9 was maintained at120° C. for 2 weeks in ion-exchanged water. The sulfonic acid equivalentweight of each electrocatalyst-coating solution was the same as itsinitial value unlike that of the electrocatalyst-coating solution II ofComparative Example 1, namely, the electrocatalyst-coating solutions ofExamples 5 to 9 were stable like the perfluorocarbon sulfonic acid(Nafion 117) electrocatalyst-coating solution. Thus, theelectrocatalyst-coating solutions of Examples 5 to 9 were excellent inboth cost and resistance to hydrolysis (durability).

Even when each of the assemblies of the sulfoalkylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane and electrodes of Examples 5 to 9 was heated at 120° C. for 2weeks together with ion-exchanged water in a Teflon-coated closedcontainer made of SUS, these assemblies were not changed unlike theassembly of the sulfonated poly(1,4-biphenylene ether ether sulfone)membrane and electrodes of Comparative Example 1, namely, the assembliesof Examples 5 to 9 were stable like the assembly of the perfluorocarbonsulfonic acid (Nafion 117) solid polymer electrolyte membrane andelectrodes. Thus, the assemblies of Examples 5 to 9 were excellent inboth cost and resistance to hydrolysis (durability).

The single cells using the sulfoalkylated poly(1,4-biphenylene etherether sulfone) solid polymer electrolyte membranes of Examples 5 to 9,respectively, were operated at 300 mA/cm² for 5,000 hours. After theoperation, the output of each single cell was the same as its initialvalue unlike that of the single cell using the sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane of Comparative Example 1, namely, the single cells of Examples5 to 9 were stable like a single cell using the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117). Thus, the singlecells of Examples 5 to 9 were excellent in both cost and resistance tohydrolysis (durability).

EXAMPLE 10

(1) Synthesis of a sulfobutylated poly(1,4-biphenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 6.00 g(0.0155 mol) of a poly(1,4-biphenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-C₆H₄-4-O—)_(n)] dried by its maintenance at110° C. for 10 hours and 150 ml of dehydrated chloroform were placed inthe flask and maintained at 60° C. for about 1 hour to effectdissolution. To the resulting solution was added 6.26 g (0.0464 mol) ofbutanesultone.

Subsequently, 6.19 g (0.0464 mol) of anhydrous aluminum chloridethoroughly ground in a mortar was added thereto with stirring over aperiod of about 30 minutes. After completion of the addition ofanhydrous aluminum chloride, the resulting mixture was refluxed withstirring at 60° C. for 20 hours. The precipitate was filtered, washedwith 150 ml of chloroform and then dried under reduced pressure. Thedried precipitate was suspended in 250 ml of water and finely ground ina mixer, and the resulting finely ground substance was filtered. Thisprocedure was repeated four times. After thorough washing with water,the water-insoluble finely ground substance thus obtained was dried at90° C. under reduced pressure. The dried substance was subjected to¹HNMR measurement to find that new peaks due to a —CH₂CH₂CH₂CH₂SO₃Hgroup were present at 1.6 to 3.8 ppm. This fact confirmed theintroduction of sulfobutyl groups.

The sulfonic acid equivalent weight of the sulfobutylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte VIthus obtained was 670 g/equivalent.

Since the sulfobutylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte VI can be produced through one step by using thepoly(1,4-biphenylene ether ether sulfone), a relatively inexpensivecommercial engineering plastic, as a starting material, the cost ofproduction thereof is as low as less than one-fiftieth that of theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

The sulfobutylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte VI is advantageous from the viewpoint of costbecause it can be produced through one step like the sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte Vand hence can be synthesized at a lower cost as compared with asulfomethylated poly(1,4-biphenylene ethyl ether sulfone) solid polymerelectrolyte and a sulfohexamethylated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte which are produced through two stepsas described hereinafter in Examples 11 and 12.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfobutylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte VI and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfobutylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte VIwas measured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfobutylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte VI was 670 g/equivalent, the same value as theinitial value, namely, the solid polymer electrolyte VI was stable likethe perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion117).

On the other hand, as described in Comparative Example 1, (1), theion-exchange group equivalent weight of the inexpensive sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte IIwas increased to 1,200 g/equivalent from its initial value of 650g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released from the solid polymerelectrolyte II.

Thus, unlike the sulfonated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte II of Comparative Example 1, the inexpensivesulfobutylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte VI was stable like the perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117) and was excellent in both cost andresistance to hydrolysis (durability).

(2) Formation of a Solid Polymer Electrolyte Membrane

The product obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membrane VIof 25 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane VI was 25 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane VI and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, the ionelectric conductivity of the electrolyte membrane VI was the same as itsinitial value like that of the perfluorocarbon sulfonic acid solidpolymer electrolyte membrane (Nafion 117) produced at a high cost, andthe solid polymer electrolyte membrane VI was firm.

On the other hand, as described in Comparative Example 1, (2), therelatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane II was broken to tatters under the same conditionsof hydrolysis by heating as above. Thus, unlike the sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane II of Comparative Example 1, the inexpensive sulfobutylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane VI was stable like the perfluorocarbon sulfonic acid solidpolymer electrolyte membrane (Nafion 117) and was excellent in both costand resistance to hydrolysis (durability).

(3) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte VI in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution VI).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution VI and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution VI after the maintenance was measured. As a result, it wasfound that the ion-exchange group equivalent weight of said solution VIwas 670 g/equivalent, the same value as the initial value, namely, thesolution VI was stable like the perfluorocarbon sulfonic acid (Nafion117) electrocatalyst-coating solution.

On the other hand, as described in Comparative Example 1, (2), theion-exchange group equivalent weight of the electrocatalyst-coatingsolution II was increased to 1,200 g/equivalent from its initial valueof 650 g/equivalent under the same conditions of hydrolysis by heatingas above, namely, sulfonic acid groups were released. Thus, unlike theelectrocatalyst-coating solution II of Comparative Example 1, theinexpensive electrocatalyst-coating solution VI was stable like theperfluorocarbon sulfonic acid (Nafion 117) electrocatalyst-coatingsolution and was excellent in both cost and resistance to hydrolysis(durability).

The aforesaid electrocatalyst-coating solution VI was applied on bothsides of the solid polymer electrolyte membrane VI obtained in the aboveitem (2), and was dried to produce a membrane-electrodes assembly VIhaving an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution II described in Comparative Example1, (2) was applied on both sides of the same solid polymer electrolytemembrane VI as that obtained in the above item (2), and was dried toproduce a membrane-electrodes assembly VI′ having an amount of platinumsupported of 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane VI as that obtainedin the above item (2), and was dried to produce a membrane-electrodesassembly VI″ having an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly VI obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly VI was not different from that before themaintenance like a membrane-electrodes assembly produced at a high costby using the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and the perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly VI′ and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. In the membrane-electrodes assemblyVI′ after the maintenance, the electrodes were peeling a little but themembrane was firm. The assembly VI′ after the maintenance hadpower-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly VI″ and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. In the membrane-electrodes assemblyVI″ after the maintenance, the electrodes were peeling a little but themembrane was firm. The assembly VI″ after the maintenance hadpower-generating capability.

On the other hand, as described in Comparative Example 1, (3), themembrane of the membrane-electrodes assembly II produced by using therelatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane II and the electrocatalyst-coating solution II wasbroken to tatters and the electrodes of the assembly were peeled, underthe same conditions of hydrolysis by heating as above.

Thus, unlike the membrane-electrodes assembly II of Comparative Example1, i.e., the assembly of the sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane and electrodes, theinexpensive assembly VI of the sulfobutylated poly(1,4-biphenylene etherether sulfone) solid polymer electrolyte membrane and electrodes wasstable like the assembly of the perfluorocarbon sulfonic acid (Nafion117) membrane and electrodes, and was excellent in both cost andresistance to hydrolysis (durability).

(4) Evaluation of the Output Capability of Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies VI, VI′ and VI″ wereallowed to absorb water by immersion in boiling deionized water for 2hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation. The output capability of thesingle cells for fuel cell thus obtained was evaluated. FIG. 7 shows acurrent density-voltage plot obtained for the thus obtained single cellfor fuel cell incorporated with the membrane-electrodes assembly VI.

The output voltage was 0.70 V at a current density of 1 A/cm² and 0.79 Vat a current density of 300 mA/cm². Thus, said single cell wassatisfactorily usable as a single cell for solid polymer electrolytefuel cell.

The above-mentioned single cells for solid polymer electrolyte fuel cellwere produced by adhering a packing material (a supporting currentcollector) of thin carbon paper to each side of each of themembrane-electrodes assemblies VI, VI′ and VI″ produced in Example 10,and providing an electroconductive separator (a bipolar plate) capableof serving as a separator between electrode chambers and passageways forgas supply to the electrodes, on the outer surface of each packingmaterial. The single cells were subjected to a long-term operation testat a current density of 300 mA/cm². The results obtained are shown inFIG. 8.

In FIG. 8, numerals 32, 33 and 34 indicate the results of the durabilitytest on the single cells for fuel cell obtained by using themembrane-electrodes assemblies VI, VI′ and VI″, respectively. In FIG. 8,numeral 35 indicates the result of the durability test on a single cellfor fuel cell obtained by using the assembly of the perfluorocarbonsulfonic acid (Nafion 117) membrane and electrodes.

In FIG. 8, numeral 32 indicates the change with time of output voltageof the single cell for fuel cell of Example 10 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 33 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 10by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

Numeral 34 indicates the change with time of output voltage of thesingle cell for fuel cell produced in Example 10 by using a solidpolymer electrolyte membrane of the polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the perfluorocarbon sulfonicacid solid polymer electrolyte (Nafion 117). Numeral 35 indicates thechange with time of output voltage of the single cell for fuel cellobtained by using the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117). Numeral 36 indicates the change withtime of output voltage of a single cell for fuel cell of ComparativeExample 10 produced by using a solid polymer electrolyte membrane of apolyether ether sulfone having sulfonic acid groups directly bondedthereto and an electrocatalyst-coating solution containing the polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

In the case of numerals 32 and 34 in FIG. 8, the initial output voltagewas 0.79 V, and the output voltage had the same value as its initialvalue even after 5,000 hours of operation. These results were equal tothose obtained by the use of the perfluorocarbon sulfonic acid solidpolymer electrolyte membrane (Nafion 117) and indicated by numeral 35 inFIG. 8.

On the other hand, the initial voltage of the single cell for fuel cellindicated by numeral 36 in FIG. 8 (the single cell for fuel cell ofComparative Example 1 obtained by using the sulfonated aromatichydrocarbon solid polymer electrolyte II) was 0.73 V, and the output ofthis single cell was zero after 600 hours of operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte VI obtainedby bonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte II having sulfonic acid groups directly bondedthereto.

The single cells for fuel cell obtained by using the membrane-electrodesassemblies VI and VI″, respectively, are superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly VI′.

That is, the electrocatalyst-coating solution VI is more suitable thanthe electrocatalyst-coating solution II, for coating an electrocatalystfor a membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 10 is higher than that of the single cell for fuel cell ofComparative Example 1 though the membrane-electrodes assemblies ofExample 10 and Comparative Example 1 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane VI and electrocatalyst-coatingsolution VI used in the membrane-electrodes assembly of Example 10 ishigher than that of the solid polymer electrolyte membrane II andelectrocatalyst-coating solution II used in the membrane-electrodesassembly of Comparative Example 1.

(5) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (4)according to the present invention. The fuel cell had an output of 3 kW.

EXAMPLE 11

(1) Synthesis of a chloromethylated poly(1,4-biphenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Thereafter,36.1 g of a poly(1,4-biphenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-O—)_(n)], 60 g (2 mols) of paraformaldehydeand 50 ml of dried nitrobenzene were placed in the flask. Then, 73 g ofhydrogen chloride gas was bubbled thereinto with stirring whilemaintaining the temperature at 100° C. After completion of the bubbling,the resulting mixture was maintained at 150° C. for 4 hours.

Subsequently, the reaction solution was slowly dropped into 1 liter ofdeionized water to precipitate a chloromethylated poly(1,4-biphenyleneether ether sulfone), which was recovered by filtration. The recoveredprecipitate was repeatedly subjected to washing with deionized water ina mixer and recovery by filtration by suction until the filtrate becameneutral. Thereafter, the precipitate thus treated was dried overnight at80° C. under reduced pressure.

(2) Synthesis of a sulfomethylated poly(1,4-biphenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Thereafter,10 g of the aforesaid chloromethylated poly(1,4-biphenylene ether ethersulfone), 50 ml of dried nitrobenzene and 30 g of sodium sulfate wereplaced in the flask and stirred at 100° C. for 5 hours. Then, 10 ml ofion-exchanged water was added thereto and stirred for 5 hours.

Subsequently, the reaction solution was slowly dropped into 1 liter ofdeionized water to precipitate a sulfomethylated poly(1,4-biphenyleneether ether sulfone), which was recovered by filtration. The recoveredprecipitate was repeatedly subjected to washing with deionized water ina mixer and recovery by filtration by suction until the filtrate becameneutral. Thereafter, the precipitate thus treated was dried overnight at120° C. under reduced pressure.

The dried precipitate was subjected to ¹HNMR measurement to find that anew peak due to a —CH₂SO₃H group was present at 4.5 ppm. This factconfirmed the introduction of sulfomethyl groups. The ion-exchange groupequivalent weight of the sulfomethylated poly(1,4-biphenylene etherether sulfone) solid polymer electrolyte VII thus obtained was 660g/equivalent.

Since the sulfomethylated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte VII can be produced by the above processthrough two steps by using the poly(1,4-biphenylene ether ethersulfone), an inexpensive commercial engineering plastic, as a startingmaterial, the cost of production thereof is as very low as less thanone-thirtieth that of the perfluorocarbon sulfonic acid solid polymerelectrolyte (Nafion 117) produced through five steps by using anexpensive starting material.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfomethylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte VII and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfomethylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte VIIwas measured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfomethylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte VII was 660 g/equivalent, the same value as theinitial value, namely, the solid polymer electrolyte VII was stable likethe perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion117).

On the other hand, as described in Comparative Example 1, (1), theion-exchange group equivalent weight of the inexpensive sulfonatedaromatic hydrocarbon solid polymer electrolyte II was increased to 1,200g/equivalent from its initial value of 650 g/equivalent under the sameconditions of hydrolysis by heating as above, namely, sulfonic acidgroups were released from the solid polymer electrolyte II.

Thus, unlike the inexpensive sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte II, the inexpensive sulfomethylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte VIIwas stable like the expensive perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117) and was excellent in both cost andresistance to hydrolysis (durability).

(3) Formation of a Solid Polymer Electrolyte Membrane

The sulfomethylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte VII obtained in the above item (2) was dissolved ina 1:1 mixed solvent of trichloroethane and dichloroethane to aconcentration of 5 wt %. The resulting solution was spread on a glassplate by spin coating, air-dried and then dried in vacuo at 80° C. toform a sulfomethylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte membrane VII of 42 μm in thickness. The ionicconductance of the obtained solid polymer electrolyte membrane VII was 7S/cm.

In a Teflon-coated closed container made of SUS, the aforesaidsulfomethylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte membrane VII and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, the ionelectric conductivity of the solid polymer electrolyte membrane VII wasthe same as its initial value like that of the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117) produced at a highcost, and the solid polymer electrolyte membrane VII was firm.

On the other hand, as described in Comparative Example 1, (2), therelatively inexpensive sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane II was broken to tattersunder the same conditions of hydrolysis by heating as above. Thus,unlike the inexpensive sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane II, the inexpensivesulfomethylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte membrane VII was stable like the expensive perfluorocarbonsulfonic acid solid polymer electrolyte membrane (Nafion 117) and wasexcellent in both cost and resistance to hydrolysis (durability).

(4) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (3), i.e., a 5 wt % solution ofthe solid polymer electrolyte VII in the trichloroethane-dichloroethanemixed solvent was added to platinum-supporting carbon (content ofplatinum supported: 40 wt %), so that the weight ratio of platinumcatalyst to the solid polymer electrolyte might be 2:1. Theplatinum-supporting carbon was uniformly dispersed in the solution toprepare a paste (an electrocatalyst-coating solution VII).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution VII and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution VII after the maintenance was measured. As a result, it wasfound that the ion-exchange group equivalent weight of theelectrocatalyst-coating solution VII was 660 g/equivalent, the samevalue as the initial value, namely, the electrocatalyst-coating solutionVII was stable like the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution.

On the other hand, as described in Comparative Example 1, (2), theion-exchange group equivalent weight of the electrocatalyst-coatingsolution II was increased to 1,200 g/equivalent from its initial valueof 650 g/equivalent under the same conditions of hydrolysis by heatingas above, namely, sulfonic acid groups were released.

Thus, unlike the electrocatalyst-coating solution II of ComparativeExample 1, the inexpensive electrocatalyst-coating solution VII wasstable like the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution and was excellent in both cost andresistance to hydrolysis (durability).

The aforesaid electrocatalyst-coating solution VII was applied on bothsides of the solid polymer electrolyte membrane VII obtained in theabove item (3), and was dried to produce a membrane-electrodes assemblyVII having an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution II described in Comparative Example1, (2) was applied on both sides of the same solid polymer electrolytemembrane VII as that obtained in the above item (2), and was dried toproduce a membrane-electrodes assembly VII′ having an amount of platinumsupported of 0.25 mg/cm². A 5 wt % solution of the perfluorocarbonsulfonic acid solid polymer electrolyte in an alcohol-water mixedsolvent was added to platinum-supporting carbon (content of platinumsupported: 40 wt %), so that the weight ratio of platinum catalyst tothe solid polymer electrolyte might be 2:1. The platinum-supportingcarbon was uniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution). This electrocatalyst-coating solutionwas applied on both sides of the same solid polymer electrolyte membraneVII as that obtained in the above item (3), and was dried to produce amembrane-electrodes assembly VII″ having an amount of platinum supportedof 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly VII obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly VII was not different from that before themaintenance like a membrane-electrodes assembly produced at a high costby using the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and the perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly VII′ and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. In the membrane-electrodes assemblyVII′ after the maintenance, the electrodes were peeling a little but themembrane was firm. The assembly VII′ after the maintenance hadpower-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly VII″ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly VII″ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly VII″ after themaintenance had power-generating capability.

On the other hand, as described in Comparative Example 1, (3), themembrane of the membrane-electrodes assembly II produced by using therelatively inexpensive sulfonated poly(1,4-biphenylene ether ethersulfone) solid polymer electrolyte membrane II and theelectrocatalyst-coating solution II was broken to tatters and theelectrodes of the assembly were peeled, under the same conditions ofhydrolysis by heating as above. Thus, unlike the membrane-electrodesassembly II of Comparative Example 1, i.e., the assembly of thesulfonated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte membrane and electrodes, the inexpensive assembly VII of thesulfomethylated poly(1,4-biphenylene ether ether sulfone) solid polymerelectrolyte membrane and electrodes was stable like the assembly of theperfluorocarbon sulfonic acid (Nafion 117) membrane and electrodes, andwas excellent in both cost and resistance to hydrolysis (durability).

(5) Evaluation of the Output Capability of Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies VII, VII′ and VII″were allowed to absorb water by immersion in boiling deionized water for2 hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation. The output capability of theresulting single cell for fuel cell incorporated with themembrane-electrodes assembly VII was evaluated. FIG. 9 shows a currentdensity-output voltage plot obtained. The output voltage was 0.65 V at acurrent density of 1 A/cm² and 0.74 V at a current density of 300mA/cm². Thus, the single cell for fuel cell incorporated with themembrane-electrodes assembly VII was satisfactorily usable as a singlecell for solid polymer electrolyte fuel cell.

The single cells for solid polymer electrolyte fuel cell obtained abovewere subjected to a long-term operation test at a current density of 300mA/cm². The results obtained are shown in FIG. 10.

In FIG. 10, numerals 37, 38 and 39 indicate the results of thedurability test on the single cells for fuel cell obtained by using theassemblies VII, VII′ and VII″, respectively, of the solid polymerelectrolyte membrane and electrodes. In FIG. 10, numeral 40 indicatesthe result of the durability test on a single cell for fuel cellobtained by using the assembly of the perfluorocarbon sulfonic acid(Nafion 117) solid polymer electrolyte membrane and electrodes.

In FIG. 10, numeral 37 indicates the change with time of output voltageof the single cell for fuel cell of Example 11 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 38 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 11by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto. Numeral 39 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 11by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117).Numeral 40 indicates the change with time of output voltage of thesingle cell for fuel cell obtained by using the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117). Numeral 41indicates the change with time of output voltage of a single cell forfuel cell of Comparative Example 11 produced by using a solid polymerelectrolyte membrane of a polyether ether sulfone having sulfonic acidgroups directly bonded thereto and an electrocatalyst-coating solutioncontaining the polyether ether sulfone solid polymer electrolyte havingsulfonic acid groups directly bonded thereto.

In the case of numerals 37 and 39 in FIG. 10, the initial voltage is0.74 V, and the voltage had the same value as the initial value evenafter 5,000 hours of operation. These results were equal to thoseobtained by the use of the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117) and indicated by numeral 40 in FIG.10.

On the other hand, the initial voltage of the single cell for fuel cellindicated by numeral 41 in FIG. 10 (the single cell for fuel cell ofComparative Example 1 obtained by using the sulfonatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane II) was 0.73 V, and the output of this single cell was zeroafter 600 hours of operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte obtained bybonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte having sulfonic acid groups directly bondedthereto.

The single cells for fuel cell obtained by using the membrane-electrodesassemblies VII and VII″, respectively, are superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly VII′. That is, the electrocatalyst-coating solution VII is moresuitable than the electrocatalyst-coating solution II, for coating anelectrocatalyst for a membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 11 is higher than that of the single cell for fuel cell ofComparative Example 1 though the membrane-electrodes assemblies ofExample 11 and Comparative Example 1 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane and electrocatalyst-coating solutionused in the membrane-electrodes assembly of Example 11 is higher thanthat of the solid polymer electrolyte membrane andelectrocatalyst-coating solution used in the membrane-electrodesassembly of Comparative Example 1.

(6) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (5)according to the present invention. The fuel cell had an output of 3 kW.

EXAMPLE 12

(1) Synthesis of a bromohexamethylated poly(1,4-biphenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Thereafter,38.8 g of a poly(1,4-biphenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-C₆H₄-4-O—)_(n)] and 50 ml of driednitrobenzene were placed in the flask. Then, 6.5 g of n-butoxylithiumwas added thereto and the resulting mixture was maintained at roomtemperature for 2 hours. Subsequently, 100 g of 1,6-dibromohexane wasadded thereto and stirred for 12 hours. The reaction solution was slowlydropped into 1 liter of deionized water to precipitate abromohexamethylated poly(1,4-biphenylene ether ether sulfone), which wasrecovered by filtration.

The recovered precipitate was repeatedly subjected to washing withdeionized water in a mixer and recovery by filtration by suction untilthe filtrate became neutral. Thereafter, the precipitate thus treatedwas dried overnight at 120° C. under reduced pressure.

(2) Synthesis of a sulfohexamethylated poly(1,4-biphenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Thereafter,10 g of the aforesaid bromohexamethylated poly(1,4-biphenylene etherether sulfone), 50 ml of dried nitrobenzene and 30 g of sodium sulfatewere placed in the flask and stirred at 100° C. for 5 hours. Then, 10 mlof ion-exchanged water was added thereto and stirred for 5 hours.

Subsequently, the reaction solution was slowly dropped into 1 liter ofdeionized water to precipitate a sulfohexamethylatedpoly(1,4-biphenylene ether ether sulfone), which was recovered byfiltration. The recovered precipitate was repeatedly subjected towashing with deionized water in a mixer and recovery by filtration bysuction until the filtrate became neutral. Thereafter, the precipitatethus treated was dried overnight at 120° C. under reduced pressure. Thedried precipitate was subjected to ¹HNMR measurement to find that newpeaks due to a —CH₂CH₂CH₂CH₂CH₂CH₂SO₃H group were present at 1.3 to 3.8ppm. This fact confirmed the introduction of sulfohexamethyl groups. Theion-exchange group equivalent weight of the sulfohexamethylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte VIIIthus obtained was 670 g/equivalent.

Since the sulfohexamethylated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte VIII can be produced by the above processthrough two steps by using the poly(1,4-biphenylene ether ethersulfone), an inexpensive commercial engineering plastic, as a startingmaterial, the cost of production thereof is as low as less thanone-thirtieth that of the perfluorocarbon sulfonic acid solid polymerelectrolyte (Nafion 117) produced through five steps by using anexpensive starting material.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfohexamethylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte VIII and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After cooling and thorough washingwith water, the ion-exchange group equivalent weight of thesulfohexamethylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte VIII was measured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfohexamethylated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte VIII was 670 g/equivalent, the same value asthe initial value, namely, the solid polymer electrolyte VIII was stablelike the perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion117).

On the other hand, as described in Comparative Example 1, (1), theion-exchange group equivalent weight of the inexpensive sulfonatedaromatic hydrocarbon solid polymer electrolyte II was increased to 1,200g/equivalent from its initial value of 650 g/equivalent under the sameconditions of hydrolysis by heating as above, namely, sulfonic acidgroups were released from the solid polymer electrolyte II. Thus, unlikethe inexpensive sulfonated poly(1,4-biphenylene ether ether sulfone)solid polymer electrolyte II, the inexpensive sulfohexamethylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolyte VIIIwas stable like the expensive perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117) and was excellent in both cost andresistance to hydrolysis (durability).

(3) Formation of a Solid Polymer Electrolyte Membrane

The product obtained in the above item (2) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %.

The resulting solution was spread on a glass plate by spin coating,air-dried and then dried in vacuo at 80° C. to form asulfohexamethylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte membrane VIII of 42 μm in thickness. The ionelectric conductivity of the obtained sulfohexamethylatedpoly(1,4-biphenylene ether ether sulfone) solid polymer electrolytemembrane VIII was 35 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaidsulfohexamethylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte membrane VIII obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, theion electric conductivity of the obtained solid polymer electrolytemembrane VIII was the same as its initial value like that of theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117), and the solid polymer electrolyte membrane VIII was firm.

On the other hand, as described in Comparative Example 1, (2), therelatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane II was broken to tatters under the same conditionsof hydrolysis by heating as above. Thus, unlike the sulfonated aromatichydrocarbon solid polymer electrolyte membrane II, the inexpensivesulfohexamethylated poly(1,4-biphenylene ether ether sulfone) solidpolymer electrolyte membrane VIII was stable like the perfluorocarbonsulfonic acid solid polymer electrolyte membrane (Nafion 117) and wasexcellent in both cost and resistance to hydrolysis (durability).

(4) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (3), i.e., a 5 wt % solution ofthe solid polymer electrolyte VIII in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution VIII).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution VIII and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution VIII after the maintenance was measured. As a result, it wasfound that the ion-exchange group equivalent weight of theelectrocatalyst-coating solution VIII was 670 g/equivalent, the samevalue as the initial value, namely, the electrocatalyst-coating solutionVIII was stable like the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution.

On the other hand, as described in Comparative Example 1, (2), theion-exchange group equivalent weight of the electrocatalyst-coatingsolution II was increased to 1,200 g/equivalent from its initial valueof 650 g/equivalent under the same conditions of hydrolysis by heatingas above, namely, sulfonic acid groups were released. Thus, unlike theelectrocatalyst-coating solution II of Comparative Example 1, theinexpensive electrocatalyst-coating solution VIII was stable like theperfluorocarbon sulfonic acid (Nafion 117) electrocatalyst-coatingsolution and was excellent in both cost and resistance to hydrolysis(durability).

The aforesaid electrocatalyst-coating solution VIII was applied on bothsides of the solid polymer electrolyte membrane obtained in the aboveitem (3), and was dried to produce a membrane-electrodes assembly VIIIhaving an amount of platinum supported of 0.25 mg/cm². Theelectrocatalyst-coating solution II described in Comparative Example 1,(2) was applied on both sides of the same solid polymer electrolytemembrane VIII as that obtained in the above item (3), and was dried toproduce a membrane-electrodes assembly VIII′ having an amount ofplatinum supported of 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane VIII as thatobtained in the above item (3), and was dried to produce amembrane-electrodes assembly VIII″ having an amount of platinumsupported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly VIII obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly VIII was not different from that before themaintenance like a membrane-electrodes assembly produced by using theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and the perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly VIII′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly VIII′ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly VIII′ after themaintenance had power-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly VIII″ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly VIII″ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly VIII″ after themaintenance had power-generating capability.

(5) Evaluation of the Output Capability of Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies VIII, VIII′ and VIII″were allowed to absorb water by immersion in boiling deionized water for2 hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated.

FIG. 11 shows a current density-voltage plot obtained for a single cellfor fuel cell produced by using the membrane-electrodes assembly VIII.The output voltage was 0.69 V at a current density of 1 A/cm² and 0.83 Vat a current density of 300 mA/cm². Thus, said single cell wassatisfactorily usable as a single cell for solid polymer electrolytefuel cell.

The single cells for solid polymer electrolyte fuel cell obtained abovewere subjected to a long-term operation test at a current density of 300mA/cm². The results obtained are shown in FIG. 12.

In FIG. 12, numerals 42, 43 and 44 indicate the results of thedurability test on the single cells for fuel cell obtained by using theassemblies VIII, VIII′ and VIII″, respectively, of the solid polymerelectrolyte membrane and electrodes. In FIG. 12, numeral 45 indicatesthe result of the durability test on a single cell for fuel cellobtained by using the assembly of the perfluorocarbon sulfonic acid(Nafion 117) solid polymer electrolyte membrane and electrodes.

In FIG. 12, numeral 42 indicates the change with time of output voltageof the single cell for fuel cell of Example 12 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 43 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 12by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto. Numeral 44 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 12by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117).Numeral 45 indicates the change with time of output voltage of thesingle cell for fuel cell obtained by using the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117). Numeral 46indicates the change with time of output voltage of a single cell forfuel cell of Comparative Example 12 produced by using a solid polymerelectrolyte membrane of a polyether ether sulfone having sulfonic acidgroups directly bonded thereto and an electrocatalyst-coating solutioncontaining the polyether ether sulfone solid polymer electrolyte havingsulfonic acid groups directly bonded thereto.

As can be seen from the results indicated by numerals 42 and 44 in FIG.12, the initial voltage of the single cells obtained by using theassemblies VIII and VIII″, respectively, of the solid polymerelectrolyte membrane of the present invention and electrodes was 0.83 V,and the single cells had the same voltage as the initial voltage evenafter 5,000 hours of operation. These results were equal to thoseobtained by the use of the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117) and indicated by numeral 45 in FIG.12.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 46 in FIG. 12 (the single cell for fuelcell of Comparative Example 1 obtained by using the sulfonated aromatichydrocarbon solid polymer electrolyte membrane) was 0.73 V, and theoutput of this single cell was zero after 600 hours of operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte obtained bybonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte having sulfonic acid groups directly bondedthereto.

The single cells for fuel cell obtained by using the membrane-electrodesassemblies VIII and VIII″, respectively, are superior in durability tothe single cell for fuel cell obtained by using the membrane-electrodesassembly VIII′. That is, the electrocatalyst-coating solution VIII ismore suitable than the electrocatalyst-coating solution II, for coatingan electrocatalyst for a membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 12 is higher than that of the single cell for fuel cell ofComparative Example 1 though the membrane-electrodes assemblies ofExample 12 and Comparative Example 1 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane and electrocatalyst-coating solutionused in the membrane-electrodes assembly of Example 12 is higher thanthat of the solid polymer electrolyte membrane andelectrocatalyst-coating solution used in the membrane-electrodesassembly of Comparative Example 1.

As can be seen from the items (1) and (2) in Examples 11, 9, 10 and 12,the values of the ion-exchange group equivalent weight (g/equivalent) ofthe sulfoalkylated poly(1,4-biphenylene ether ether sulfone) solidelectrolytes of the above formula [3] in which the values of n (thenumber of carbon atoms of the alkylene group) are 1, 3, 4 and 6 are 660,680, 670 and 670, respectively, which are substantially the same. Thevalues of ionic conductance (S/cm) of the solid polymer electrolytemembranes obtained by using these solid electrolytes are 7, 15, 25 and35, respectively. That is, with an increase of the value of n in thesulfoalkylated aromatic hydrocarbon solid electrolytes, the ionicconductance and the proton transportability increase, so that anexcellent solid polymer electrolyte fuel cell can be obtained.

On the other hand, from the viewpoint of cost, the sulfopropylatedpoly(1,4-biphenylene ether ether sulfone) solid electrolyte and thesulfobutylated poly(1,4-biphenylene ether ether sulfone) solidelectrolyte, which can be synthesized by a one-stage reaction with asultone, are more advantageous than the sulfohexamethylatedpoly(1,4-biphenylene ether ether sulfone) solid electrolyte and thesulfomethylated poly(1,4-biphenylene ether ether sulfone) solidelectrolyte, which are synthesized by a two-stage reaction. The value ofn is preferably 3 or 4 for reconciling the ionic conductance and thecost.

(6) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (5)according to the present invention. The fuel cell had an output of 3 kW.

EXAMPLE 13

(1) Synthesis of a sulfopropylated poly(1,4-phenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 4.84 g(0.0155 mol) of a poly(1,4-phenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-O—)_(n)] dried by its maintenance at 110° C.for 10 hours and 150 ml of dehydrated chloroform were placed in theflask and maintained at 60° C. for about 1 hour to effect dissolution.To the resulting solution was added 5.67 g (0.0464 mol) ofpropanesultone.

Subsequently, 6.19 g (0.0464 mol) of anhydrous aluminum chloridethoroughly ground in a mortar was added thereto with stirring over aperiod of about 30 minutes. After completion of the addition ofanhydrous aluminum chloride, the resulting mixture was refluxed withstirring at 60° C. for 30 hours. The polymer precipitated was filtered,washed with 150 ml of chloroform and then dried under reduced pressure.The dried polymer was suspended in 250 ml of water and finely ground ina mixer, and the resulting finely ground substance was filtered. Thisprocedure was repeated four times. After thorough washing with water,the water-insoluble finely ground substance thus obtained was dried at90° C. under reduced pressure.

The dried substance was subjected to ¹HNMR measurement to find that newpeaks due to a —CH₂CH₂CH₂SO₃H group were present at 2.2 ppm and 3.8 ppm.This fact confirmed the introduction of sulfopropyl groups.

The sulfonic acid equivalent weight of the sulfopropylatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte IXthus obtained was 670 g/equivalent.

Since the sulfopropylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte IX can be produced through one step by using thepoly(1,4-phenylene ether ether sulfone), a relatively inexpensivecommercial engineering plastic, as a starting material, the cost ofproduction thereof is as low as less than one-fiftieth that of theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfopropylated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte IX and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfopropylatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte IX wasmeasured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfopropylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte IX was 670 g/equivalent, the same value as theinitial value, namely, the solid polymer electrolyte IX was stable likethe perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion117).

On the other hand, as described hereinafter in Comparative Example 2,(1), the ion-exchange group equivalent weight of an inexpensivesulfonated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte X was increased to 1,250 g/equivalent from its initial valueof 660 g/equivalent under the same conditions of hydrolysis by heatingas above, namely, sulfonic acid groups were released from the solidpolymer electrolyte X. Thus, unlike the sulfonated poly(1,4-phenyleneether ether sulfone) solid polymer electrolyte X described hereinafterin Comparative Example 2, the inexpensive sulfopropylatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte IX wasstable like the perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117) and was excellent in both cost and resistance to hydrolysis(durability).

(2) Formation of a Solid Polymer Electrolyte Membrane

The product obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membrane IXof 25 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane IX was 15 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane IX obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, theion electric conductivity of the solid polymer electrolyte membrane IXobtained was the same as its initial value like that of theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117), and the solid polymer electrolyte membrane IX was firm.

On the other hand, as described hereinafter in Comparative Example 2,(2), the relatively inexpensive sulfonated aromatic hydrocarbon solidpolymer electrolyte membrane X was broken to tatters under the sameconditions of hydrolysis by heating as above. Thus, unlike thesulfonated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte membrane X described hereinafter in Comparative Example 2,(2), the inexpensive sulfopropylated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte membrane IX was stable like theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and was excellent in both cost and resistance to hydrolysis(durability).

(3) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte IX in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution IX).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution IX and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution IX after the maintenance was measured. As a result, it wasfound that the ion-exchange group equivalent weight of theelectrocatalyst-coating solution IX was 670 g/equivalent, the same valueas the initial value, namely, the electrocatalyst-coating solution IXwas stable like the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution.

On the other hand, as described hereinafter in Comparative Example 2,(2), the ion-exchange group equivalent weight of theelectrocatalyst-coating solution X was increased to 1,250 g/equivalentfrom its initial value of 660 g/equivalent under the same conditions ofhydrolysis by heating as above, namely, sulfonic acid groups werereleased. Thus, unlike the electrocatalyst-coating solution X describedherein-after in Comparative Example 2, (2), the inexpensiveelectrocatalyst-coating solution IX was stable like the perfluorocarbonsulfonic acid (Nafion 117) electrocatalyst-coating solution and wasexcellent in both cost and resistance to hydrolysis (durability).

The aforesaid electrocatalyst-coating solution IX was applied on bothsides of the solid polymer electrolyte membrane IX obtained in the aboveitem (2), and was dried to produce a membrane-electrodes assembly IXhaving an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution X described hereinafter inComparative Example 2, (2) was applied on both sides of the same solidpolymer electrolyte membrane IX as that obtained in the above item (2),and was dried to produce a membrane-electrodes assembly IX′ having anamount of platinum supported of 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane IX as that obtainedin the above item (2), and was dried to produce a membrane-electrodesassembly IX″ having an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly IX obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly IX was not different from that before themaintenance like a membrane-electrodes assembly produced by using theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and the perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly IX′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly IX′ after the maintenance, the electrodes were peeling a littlebut the membrane was firm. The assembly IX′ after the maintenance hadpower-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly IX″ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly IX″ after the maintenance, the electrodes were peeling a littlebut the membrane was firm. The assembly IX″ after the maintenance hadpower-generating capability.

On the other hand, as described hereinafter in Comparative Example 2,(3), the membrane of a membrane-electrodes assembly X produced by usingthe relatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane X and the electrocatalyst-coating solution X wasbroken to tatters and the electrodes of the assembly were peeled, underthe same conditions of hydrolysis by heating as above.

Thus, unlike the inexpensive membrane-electrodes assembly X describedhereinafter in Comparative Example 2, (3), i.e., the assembly of thesulfonated aromatic hydrocarbon solid polymer electrolyte membrane andelectrodes, the inexpensive assembly IX of the sulfopropylatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolytemembrane and electrodes was stable like the assembly of theperfluorocarbon sulfonic acid (Nafion 117) membrane and electrodes, andwas excellent in both cost and resistance to hydrolysis (durability).

(4) Durability Test on Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies IX, IX′ and IX″ wereallowed to absorb water by immersion in boiling deionized water for 2hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated.

In detail, the single cell for solid polymer electrolyte fuel cell shownin FIG. 1 was produced by adhering a packing material (a supportingcurrent collector) 5 of thin carbon paper to each of the electrodes ofeach membrane-electrodes assembly 4 obtained in Example 13 and composedof a solid polymer electrolyte membrane 1, an oxygen electrode 2 and ahydrogen electrode 3, and providing an electroconductive separator (abipolar plate) 6 capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material. The single cells for fuel cells thusobtained were subjected to a long-term deterioration test at a currentdensity of 300 mA/cm². The results obtained are shown in FIG. 13.

In FIG. 13, numerals 47, 48 and 49 indicate the results of thedurability test on the single cells for fuel cell obtained by using theassemblies IX, IX′ and IX″, respectively, of the solid polymerelectrolyte membrane and electrodes.

In FIG. 13, numeral 50 indicates the result of the durability test on asingle cell for fuel cell obtained by using the assembly of theperfluorocarbon sulfonic acid (Nafion 117) solid polymer electrolytemembrane and electrodes.

In FIG. 13, numeral 47 indicates the change with time of output voltageof the single cell for fuel cell of Example 13 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 48 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 13by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto. Numeral 49 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 13by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117).Numeral 50 indicates the change with time of output voltage of thesingle cell for fuel cell obtained by using the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117). Numeral 51indicates the change with time of output voltage of a single cell forfuel cell of Comparative Example 13 produced by using a solid polymerelectrolyte membrane of a polyether ether sulfone having sulfonic acidgroups directly bonded thereto and an electrocatalyst-coating solutioncontaining the polyether ether sulfone solid polymer electrolyte havingsulfonic acid groups directly bonded thereto.

As can be seen from the results indicated by numerals 47 and 49 in FIG.13, the initial voltage of the single cells obtained by using theassemblies IX and IX″, respectively, of the solid polymer electrolytemembrane of the present invention and electrodes was 0.79 V, and thesingle cells had the same voltage as the initial voltage even after5,000 hours of operation. These results were equal to those obtained bythe use of the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and indicated by numeral 50 in FIG. 13.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 51 in FIG. 13 (the single cell for fuelcell obtained by using the sulfonated aromatic hydrocarbon solid polymerelectrolyte X which is described hereinafter in Comparative Example 2)was 0.73 V, and the output of this single cell was zero after 600 hoursof operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte obtained bybonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte having sulfonic acid groups directly bondedthereto.

The single cells for fuel cell obtained by using the membrane-electrodesassemblies IX and IX″, respectively, are superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly IX′. That is, the electrocatalyst-coating solution IX is moresuitable than the electrocatalyst-coating solution X, for coating anelectrocatalyst for a membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 13 is higher than that of the single cell for fuel cell ofComparative Example 2 though the membrane-electrodes assemblies ofExample 13 and Comparative Example 2 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane and electrocatalyst-coating solutionused in the membrane-electrodes assembly of Example 13 is higher thanthat of the solid polymer electrolyte membrane andelectrocatalyst-coating solution used in the membrane-electrodesassembly of Comparative Example 2.

(5) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (4)according to the present invention. The fuel cell had an output of 3 kW.

Comparative Example 2

(1) Synthesis of a sulfonated poly(1,4-phenylene ether ether sulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 3.22 g(0.0103 mol) of a poly(1,4-phenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-O—)_(n)] dried by its maintenance at 110° C.for 10 hours and 100 ml of chloroform were placed in the flask andmaintained at 60° C. for about 1 hour to effect dissolution.

To the resulting solution was added a solution of 1.165 g (0.01 mol) ofchlorosulfonic acid in 50 ml of 1,1,2,2-tetrachloroethane over a periodof about 10 minutes. The resulting mixture was stirred at 60° C. for 4hours. The precipitate was filtered and then washed with 150 ml ofchloroform. The washed precipitate was dissolved in 250 ml of methanolat 60° C. The resulting solution was dried at 60° C. under reducedpressure. The polymer thus obtained was finely ground in a mixertogether with 250 ml of water, and the resulting mixture was filtered.This procedure was repeated three times.

The water-insoluble fine powder thus obtained was dried over phosphoruspentaoxide at 90° C. under reduced pressure. This fine powder wasinsoluble in water and soluble in methanol.

The dried fine powder was subjected to ¹HNMR measurement to find thatabsorptions at 7.3 to 8.0 ppm due to the hydrogen atoms of the phenylgroups in the starting poly(1,4-phenylene ether ether sulfone) had beendecreased, and that a new absorption due to the hydrogen atom of aphenyl group adjacent to a SO₃H group was present at 8.3 ppm. This factconfirmed the introduction of sulfonic acid groups. The sulfonic acidequivalent weight of the sulfonated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte X thus obtained was 660 g/equivalent.

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidsulfonated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte X obtained and 20 ml of ion-exchanged water were maintainedat 120° C. for 2 weeks. After cooling and thorough washing with water,the ion-exchange group equivalent weight of the sulfonatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte X wasmeasured. As a result, it was found that the sulfonic acid equivalentweight of the sulfonated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte X had been increased to 1,250 g/equivalent from itsinitial value of 660 g/equivalent, namely, sulfonic acid groups had beenreleased.

(2) Formation of a Solid Polymer Electrolyte Membrane

The sulfonated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte X obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membrane Xof 45 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane X was 8 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane X obtained and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. As a result, the solid polymerelectrolyte membrane X was broken to tatters.

(3) Production of an Electrocatalyst-coating Solution and aMembrane-electrodes Assembly

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte X in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution X).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution X and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution X after the maintenance was measured. As a result, it was foundthat the ion-exchange group equivalent weight of theelectrocatalyst-coating solution X had been increased to 1,250g/equivalent from its initial value of 660 g/equivalent, namely,sulfonic acid groups had been released.

The aforesaid electrocatalyst-coating solution X was applied on bothsides of the solid polymer electrolyte membrane X obtained in the aboveitem (2), and was dried to produce a membrane-electrodes assembly Xhaving an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly X obtained and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. As a result, the membrane of themembrane-electrodes assembly X was broken to tatters and its electrodeswere peeled.

(4) Durability Test on a Single Cell for Fuel Cell

A single cell for solid polymer electrolyte fuel cell was produced byadhering a packing material (a supporting current collector) of thincarbon paper to each side of the membrane-electrodes assembly X ofComparative Example 2, and providing an electroconductive separator (abipolar plate) capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material. The single cell was subjected to along-term operation test at a current density of 300 mA/cm². As aresult, it was found that as indicated by numeral 51 in FIG. 13, theinitial output voltage of the single cell was 0.73 V and that the outputvoltage of the single cell was zero after 600 hours of operation.

EXAMPLE 14

(1) Synthesis of a sulfobutylated poly(1,4-phenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 4.84 g(0.0155 mol) of a poly(1,4-phenylene ether ether sulfone)[(—C₆H₄-4-SO2C₆H₄-4-OC₆H₄-4-O—)_(n)] dried by its maintenance at 110° C.for 10 hours and 150 ml of dehydrated chloroform were placed in theflask and maintained at 60° C. for about 1 hour to effect dissolution.To the resulting solution was added 6.26 g (0.0464 mol) ofbutanesultone. Subsequently, 6.19 g (0.0464 mol) of anhydrous aluminumchloride thoroughly ground in a mortar was added thereto with stirringover a period of about 30 minutes. After completion of the addition ofanhydrous aluminum chloride, the resulting mixture was refluxed withstirring at 60° C. for 30 hours. The polymer precipitated was filtered,washed with 150 ml of chloroform and then dried under reduced pressure.The dried polymer was suspended in 250 ml of water and finely ground ina mixer, and the resulting finely ground substance was filtered. Thisprocedure was repeated four times. After thorough washing with water,the water-insoluble finely ground substance thus obtained was dried at90° C. under reduced pressure.

The dried substance was subjected to ¹HNMR measurement to find that newpeaks due to a —CH₂CH₂CH₂CH₂SO₃H group were present at 1.3 to 3.8 ppm.This fact confirmed the introduction of sulfobutyl groups. The sulfonicacid equivalent weight of the sulfobutylated poly(1,4-phenylene etherether sulfone) solid polymer electrolyte XI thus obtained was 650g/equivalent.

Since the sulfobutylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte XI can be produced through one step by using thepoly(1,4-phenylene ether ether sulfone), a relatively inexpensivecommercial engineering plastic, as a starting material, the cost ofproduction thereof is as low as less than one-fiftieth that of theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfobutylated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte XI and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfobutylatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte XI wasmeasured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfobutylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte XI was 650 g/equivalent, the same value as theinitial value, namely, the solid polymer electrolyte XI was stable likethe perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion117).

On the other hand, as described in Comparative Example 2, (1), theion-exchange group equivalent weight of the inexpensive sulfonatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte X wasincreased to 1,250 g/equivalent from its initial value of 660g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released from the solid polymerelectrolyte X.

Thus, unlike the inexpensive sulfonated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte X described in Comparative Example 2,(1), the inexpensive sulfobutylated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte XI was stable like theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117) andwas excellent in both cost and resistance to hydrolysis (durability).

(2) Formation of a Solid Polymer Electrolyte Membrane

The product obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membrane XIof 25 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane XI was 25 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane XI obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, theion electric conductivity of the obtained solid polymer electrolytemembrane XI was the same as its initial value like that of theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117), and the solid polymer electrolyte membrane XI was firm.

On the other hand, the relatively inexpensive sulfonated aromatichydrocarbon solid polymer electrolyte membrane X of Comparative Example2 was broken to tatters under the same conditions of hydrolysis byheating as above. Thus, unlike the sulfonated poly(1,4-phenylene etherether sulfone) solid polymer electrolyte membrane X of ComparativeExample 2, the inexpensive sulfobutylated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte membrane XI was stable like theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and was excellent in both cost and resistance to hydrolysis(durability).

(3) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte XI in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution XI).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution XI and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution XI after maintenance was measured. As a result, it was foundthat the ion-exchange group equivalent weight of theelectrocatalyst-coating solution XI was 650 g/equivalent, the same valueas the initial value, namely, the electrocatalyst-coating solution XIwas stable like the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution.

On the other hand, as described in Comparative Example 2, (2), theion-exchange group equivalent weight of the electrocatalyst-coatingsolution X was increased to 1,250 g/equivalent from its initial value of660 g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released. Thus, unlike theelectrocatalyst-coating solution X of Comparative Example 2, theinexpensive electrocatalyst-coating solution XI was stable like theperfluorocarbon sulfonic acid (Nafion 117) electrocatalyst-coatingsolution and was excellent in both cost and resistance to hydrolysis(durability).

The aforesaid electrocatalyst-coating solution XI was applied on bothsides of the solid polymer electrolyte membrane XI obtained in the aboveitem (2), and was dried to produce a membrane-electrodes assembly XIhaving an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution X of Comparative Example 2 wasapplied on both sides of the same solid polymer electrolyte membrane XIas that obtained in the above item (2), and was dried to produce amembrane-electrodes assembly XI′ having an amount of platinum supportedof 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane XI as that obtainedin the above item (2), and was dried to produce a membrane-electrodesassembly XI″ having an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XI obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly XI was not different from that before themaintenance like a membrane-electrodes assembly produced by using theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and the perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XI′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly XI′ after the maintenance, the electrodes were peeling a littlebut the membrane was firm. The assembly XI′ after the maintenance hadpower-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XI″ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly XI″ after the maintenance, the electrodes were peeling a littlebut the membrane was firm. The assembly XI″ after the maintenance hadpower-generating capability.

On the other hand, as described in Comparative Example 2, (3), themembrane of the membrane-electrodes assembly X produced by using therelatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane X and the electrocatalyst-coating solution X wasbroken to tatters and the electrodes of the assembly were peeled, underthe same conditions of hydrolysis by heating as above. Thus, unlike themembrane-electrodes assembly X of Comparative Example 2, i.e., theassembly of the sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane and electrodes, the inexpensive assembly XI of thesulfobutylated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte membrane and electrodes was stable like the assembly of theperfluorocarbon sulfonic acid (Nafion 117) membrane and electrodes, andwas excellent in both cost and resistance to hydrolysis (durability).

(4) Durability Test on Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies XI, XI′ and XI″ wereallowed to absorb water by immersion in boiling deionized water for 2hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated.

In detail, the single cell for solid polymer electrolyte fuel cell shownin FIG. 1 was produced by adhering a packing material (a supportingcurrent collector) 5 of thin carbon paper to each of the electrodes ofeach membrane-electrodes assembly 4 obtained in Example 14 and composedof a solid polymer electrolyte membrane 1, an oxygen electrode 2 and ahydrogen electrode 3, and providing an electroconductive separator (abipolar plate) 6 capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material. The single cells for fuel cells thusobtained were subjected to a long-term deterioration test at a currentdensity of 300 mA/cm². The results obtained are shown in FIG. 14.

In FIG. 14, numerals 52, 53 and 54 indicate the results of thedurability test on the single cells for fuel cell obtained by using theassemblies XI, XI′ and XI″, respectively, of the solid polymerelectrolyte membrane and electrodes.

In FIG. 14, numeral 55 indicates the result of the durability test on asingle cell for fuel cell obtained by using the assembly of theperfluorocarbon sulfonic acid (Nafion 117) solid polymer electrolytemembrane and electrodes.

In FIG. 14, numeral 52 indicates the change with time of output voltageof the single cell for fuel cell of Example 14 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 53 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 14by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto. Numeral 54 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 14by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117).Numeral 55 indicates the change with time of output voltage of thesingle cell for fuel cell obtained by using the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117). Numeral 56indicates the change with time of output voltage of a single cell forfuel cell of Comparative Example 14 produced by using a solid polymerelectrolyte membrane of a polyether ether sulfone having sulfonic acidgroups directly bonded thereto and an electrocatalyst-coating solutioncontaining the polyether ether sulfone solid polymer electrolyte havingsulfonic acid groups directly bonded thereto.

As can be seen from the results indicated by numerals 52 and 54 in FIG.14, the initial voltage of the single cells obtained by using theassemblies XI and XI″, respectively, of the solid polymer electrolytemembrane of the present invention and electrodes was 0.79 V, and thesingle cells had the same voltage as the initial voltage even after5,000 hours of operation. These results were equal to those obtained bythe use of the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and indicated by numeral 55 in FIG. 14.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 56 in FIG. 14 (the single cell for fuelcell of Comparative Example 2 obtained by using the sulfonated aromatichydrocarbon solid polymer electrolyte X) was 0.73 V, and the output ofthis single cell was zero after 600 hours of operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte obtained bybonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte having sulfonic acid groups directly bondedthereto.

The single cell for fuel cell obtained by using the membrane-electrodesassembly XI of the present invention is superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly XI′. That is, the electrocatalyst-coating solution XI is moresuitable than the electrocatalyst-coating solution X, for coating anelectrocatalyst for a membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 14 is higher than that of the single cell for fuel cell ofComparative Example 2 though the membrane-electrodes assemblies ofExample 14 and Comparative Example 2 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane and electrocatalyst-coating solutionused in the membrane-electrodes assembly of Example 14 is higher thanthat of the solid polymer electrolyte membrane andelectrocatalyst-coating solution used in the membrane-electrodesassembly of Comparative Example 2.

(5) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (4)according to the present invention. The fuel cell had an output of 3 kW.

EXAMPLE 15

(1) Synthesis of a chloromethylated poly(1,4-phenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Thereafter,36.1 g of a poly(1,4-phenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4—OC₆H₄-4-O—)_(n)], 60 g (2 mols) of paraformaldehydeand 50 ml of dried nitrobenzene were placed in the flask. Then, 73 g ofhydrogen chloride gas was bubbled thereinto with stirring whilemaintaining the temperature at 100° C. After completion of the bubbling,the resulting mixture was maintained at 150° C. for 4 hours.

Subsequently, the reaction solution was slowly dropped into 1 liter ofdeionized water to precipitate a chloromethylated poly(1,4-phenyleneether ether sulfone), which was recovered by filtration. The recoveredprecipitate was repeatedly subjected to washing with deionized water ina mixer and recovery by filtration by suction until the filtrate becameneutral. Thereafter, the precipitate thus treated was dried overnight at80° C. under reduced pressure.

(2) Synthesis of a sulfomethylated poly(1,4-phenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Thereafter,10 g of the aforesaid chloromethylated poly(1,4-phenylene ether ethersulfone), 50 ml of dried nitrobenzene and 30 g of sodium sulfate wereplaced in the flask and stirred at 100° C. for 5 hours. Then, 10 ml ofion-exchanged water was added thereto and stirred for 5 hours.

Subsequently, the reaction solution was slowly dropped into 1 liter ofdeionized water to precipitate a sulfomethylated poly(1,4-phenyleneether ether sulfone) XII, which was recovered by filtration. Therecovered precipitate was repeatedly subjected to washing with deionizedwater in a mixer and recovery by filtration by suction until thefiltrate became neutral. Thereafter, the precipitate thus treated wasdried overnight at 120° C. under reduced pressure.

The dried precipitate was subjected to ¹HNMR measurement to find that anew peak due to a —CH₂SO₃H group was present at 2.2 ppm. Theion-exchange group equivalent weight of the sulfomethylatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte XIIthus obtained was 650 g/equivalent.

Since the sulfomethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte XII can be produced by the above process through twosteps by using the poly(1,4-phenylene ether ether sulfone), aninexpensive commercial engineering plastic, as a starting material, thecost of production thereof is as very low as less than one-thirtieththat of the perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117) produced through five steps.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfomethylated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte XII and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfomethylatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte XIIwas measured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfomethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte XII was 650 g/equivalent, the same value as theinitial value, namely, the solid polymer electrolyte XII was stable likethe perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion117).

On the other hand, as described in Comparative Example 2, (1), theion-exchange group equivalent weight of the inexpensive sulfonatedaromatic hydrocarbon solid polymer electrolyte X was increased to 1,250g/equivalent from its initial value of 660 g/equivalent under the sameconditions of hydrolysis by heating as above, namely, sulfonic acidgroups were released from the solid polymer electrolyte X. Thus, unlikethe sulfonated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte X, the inexpensive sulfomethylated poly(1,4-phenylene etherether sulfone) solid polymer electrolyte XII was stable like theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117) andwas excellent in both cost and resistance to hydrolysis (durability).

(3) Formation of a Solid Polymer Electrolyte Membrane

The sulfomethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte XII obtained in the above item (2) was dissolved ina 1:1 mixed solvent of trichloroethane and dichloroethane to aconcentration of 5 wt %. The resulting solution was spread on a glassplate by spin coating, air-dried and then dried in vacuo at 80° C. toform a sulfomethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte membrane XII of 42 μm in thickness. The ionicconductance of the obtained solid polymer electrolyte membrane XII was 5S/cm.

In a Teflon-coated closed container made of SUS, the aforesaidsulfomethylated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte membrane XII and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, the ionelectric conductivity of the solid polymer electrolyte membrane XII wasthe same as its initial value like that of the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117), and the solidpolymer electrolyte membrane XII was firm.

On the other hand, as described in Comparative Example 2, (2), therelatively inexpensive sulfonated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte membrane X was broken to tattersunder the same conditions of hydrolysis by heating as above. Thus,unlike the inexpensive sulfonated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte membrane X, the inexpensivesulfomethylated poly(1,4-phenylene ether ether sulfone) solid polymerelectrolyte membrane XII was stable like the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117) and was excellentin both cost and resistance to hydrolysis (durability).

(4) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (3), i.e., a 5 wt % solution ofthe solid polymer electrolyte XII in the trichloroethane-dichloroethanemixed solvent was added to platinum-supporting carbon (content ofplatinum supported: 40 wt %), so that the weight ratio of platinumcatalyst to the solid polymer electrolyte might be 2:1. Theplatinum-supporting carbon was uniformly dispersed in the solution toprepare a paste (an electrocatalyst-coating solution XII).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution XII and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution XII after the maintenance was measured. As a result, it wasfound that the ion-exchange group equivalent weight of theelectrocatalyst-coating solution XII was 650 g/equivalent, the samevalue as the initial value, namely, the electrocatalyst-coating solutionXII was stable like the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution.

On the other hand, as described in Comparative Example 2, (2), theion-exchange group equivalent weight of the electrocatalyst-coatingsolution X was increased to 1,250 g/equivalent from its initial value of660 g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released. Thus, unlike theinexpensive electrocatalyst-coating solution X described in ComparativeExample 2, (2), the inexpensive electrocatalyst-coating solution XII wasstable like the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution and was excellent in both cost andresistance to hydrolysis (durability).

The aforesaid electrocatalyst-coating solution XII was applied on bothsides of the solid polymer electrolyte membrane XII obtained in theabove item (3), and was dried to produce a membrane-electrodes assemblyXII having an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution X described in Comparative Example2, (2) was applied on both sides of the same solid polymer electrolytemembrane XII as that obtained in the above item (3), and was dried toproduce a membrane-electrodes assembly XII′ having an amount of platinumsupported of 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte (Nafion 117) in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane XII as thatobtained in the above item (3), and was dried to produce amembrane-electrodes assembly XII″ having an amount of platinum supportedof 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XII obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly XII was not different from that before themaintenance like a membrane-electrodes assembly produced by using theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and the perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XII′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly XII′ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly XII′ after themaintenance had power-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XII″ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly XII″ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly XII″ after themaintenance had power-generating capability.

On the other hand, as described in Comparative Example 2, (3), themembrane of the membrane-electrodes assembly X produced by using therelatively inexpensive sulfonated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte membrane X and theelectrocatalyst-coating solution X was broken to tatters and theelectrodes of the assembly were peeled, under the same conditions ofhydrolysis by heating as above.

Thus, unlike the membrane-electrodes assembly X of Comparative Example2, i.e., the assembly of the sulfonated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte membrane and electrodes, theinexpensive assembly XII of the sulfomethylated poly(1,4-phenylene etherether sulfone) solid polymer electrolyte membrane and electrodes wasstable like the assembly of the perfluorocarbon sulfonic acid (Nafion117) membrane and electrodes, and was excellent in both cost andresistance to hydrolysis (durability).

(5) Durability Test on Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies XII, XII′ and XII″were allowed to absorb water by immersion in boiling deionized water for2 hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation. The output capability of theresulting single cell for fuel cell was evaluated.

In detail, the single cell for solid polymer electrolyte fuel cell shownin FIG. 1 was produced by adhering a packing material (a supportingcurrent collector) 5 of thin carbon paper to each of the electrodes ofeach membrane-electrodes assembly 4 obtained in Example 15 and composedof a solid polymer electrolyte membrane 1, an oxygen electrode 2 and ahydrogen electrode 3, and providing an electroconductive separator (abipolar plate) 6 capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material. The single cells for solid polymerelectrolyte fuel cell thus obtained were subjected to a long-termdeterioration test at a current density of 300 mA/cm². The results areshown in FIG. 15.

In FIG. 15, numerals 57, 58 and 59 indicate the results of thedurability test on the single cells for fuel cell obtained by using theassemblies XII, XII′ and XII″, respectively, of the solid polymerelectrolyte membrane and electrodes.

In FIG. 15, numeral 60 indicates the result of the durability test on asingle cell for fuel cell obtained by using the assembly of theperfluorocarbon sulfonic acid (Nafion 117) solid polymer electrolytemembrane and electrodes.

In FIG. 15, numeral 57 indicates the change with time of output voltageof the single cell for fuel cell of Example 15 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 58 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 15by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

Numeral 59 indicates the change with time of output voltage of thesingle cell for fuel cell produced in Example 15 by using a solidpolymer electrolyte membrane of the polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the perfluorocarbon sulfonicacid solid polymer electrolyte (Nafion 117). Numeral 60 indicates thechange with time of output voltage of the single cell for fuel cellobtained by using the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117). Numeral 61 indicates the change withtime of output voltage of a single cell for fuel cell of ComparativeExample 15 produced by using a solid polymer electrolyte membrane of apolyether ether sulfone having sulfonic acid groups directly bondedthereto and an electrocatalyst-coating solution containing the polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto.

As can be seen from the results indicated by numerals 57 and 59 in FIG.15, the initial voltage of the single cells obtained by using theassemblies XII and XII″, respectively, of the solid polymer electrolytemembrane of the present invention and electrodes was 0.74 V, and thesingle cells had the same voltage as the initial voltage even after5,000 hours of operation. These results were equal to those obtained bythe use of the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and indicated by numeral 60 in FIG. 15.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 61 in FIG. 15 (the single cell for fuelcell of Comparative Example 2 obtained by using the sulfonated aromatichydrocarbon solid polymer electrolyte membrane) was 0.73 V, and theoutput of this single cell was zero after 600 hours of operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte obtained bybonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte having sulfonic acid groups directly bondedthereto.

The single cell for fuel cell obtained by using the membrane-electrodesassembly XII of the present invention is superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly XII′. That is, the electrocatalyst-coating solution XII is moresuitable than the electrocatalyst-coating solution X, for coating anelectrocatalyst for a membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 15 is higher than that of the single cell for fuel cell ofComparative Example 2 though the membrane-electrodes assemblies ofExample 15 and Comparative Example 2 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane and electrocatalyst-coating solutionused in the membrane-electrodes assembly of Example 15 is higher thanthat of the solid polymer electrolyte membrane andelectrocatalyst-coating solution used in the membrane-electrodesassembly of Comparative Example 2.

(6) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (5)according to the present invention. The fuel cell had an output of 3 kw.

EXAMPLE 16

(1) Synthesis of a bromohexamethylated poly(1,4-phenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Thereafter,38.8 g of a poly(1,4-phenylene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-4-OC₆H₄-4-C₆H₄-4-O—)_(n)] and 50 ml of driednitrobenzene were placed in the flask. Then, 6.5 g of n-butoxylithiumwas added thereto and the resulting mixture was maintained at roomtemperature for 2 hours. Subsequently, 100 g of 1,6-dibromohexane wasadded thereto and stirred for 12 hours.

The reaction solution was slowly dropped into 1 liter of deionized waterto precipitate a bromohexamethylated poly(1,4-phenylene ether ethersulfone), which was recovered by filtration. The recovered precipitatewas repeatedly subjected to washing with deionized water in a mixer andrecovery by filtration by suction until the filtrate became neutral. Theprecipitate thus treated was dried overnight at 120° C. under reducedpressure.

(2) Synthesis of a sulfohexamethylated poly(1,4-phenylene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Thereafter,10 g of the aforesaid bromohexamethylated poly(1,4-phenylene ether ethersulfone), 50 ml of dried nitrobenzene and 30 g of sodium sulfate wereplaced in the flask and stirred at 100° C. for 5 hours. Then, 10 ml ofion-exchanged water was added thereto and stirred for 5 hours.

Subsequently, the reaction solution was slowly dropped into 1 liter ofdeionized water to precipitate a sulfohexamethylated poly(1,4-phenyleneether ether sulfone), which was recovered by filtration. The recoveredprecipitate was repeatedly subjected to washing with deionized water ina mixer and recovery by filtration by suction until the filtrate becameneutral. The precipitate thus treated was dried overnight at 120° C.under reduced pressure.

The dried precipitate was subjected to ¹HNMR measurement to find thatnew peaks due to a —CH₂CH₂CH₂CH₂CH₂CH₂SO₃H group were present at 1.3 to4.6 ppm. This fact confirmed the introduction of sulfohexamethyl groups.The ion-exchange group equivalent weight of the sulfohexamethylatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte XIIIthus obtained was 660 g/equivalent.

Since the sulfohexamethylated poly(1,4-phenylene ether ether sulfone)solid polymer electrolyte XIII can be produced by the above processthrough two steps by using the poly(1,4-phenylene ether ether sulfone),an inexpensive commercial engineering plastic, as a starting material,the cost of production thereof is as low as less than one-thirtieth thatof the perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion117) produced through five steps by using an expensive startingmaterial.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfohexamethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte XIII and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After cooling and thorough washingwith water, the ion-exchange group equivalent weight of thesulfohexamethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte XIII was measured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfohexamethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte XIII was 660 g/equivalent, the same value as theinitial value, namely, the solid polymer electrolyte XIII was stablelike the perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion117).

On the other hand, as described in Comparative Example 2, (1), theion-exchange group equivalent weight of the inexpensive sulfonatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolyte X wasincreased to 1,250 g/equivalent from its initial value of 660g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released from the solid polymerelectrolyte X.

Thus, unlike the inexpensive sulfonated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte X, the inexpensivesulfohexamethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte XIII was stable like the perfluorocarbon sulfonicacid solid polymer electrolyte (Nafion 117) and was excellent in bothcost and resistance to hydrolysis (durability).

(3) Formation of a Solid Polymer Electrolyte Membrane

The product obtained in the above item (2) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a sulfohexamethylatedpoly(1,4-phenylene ether ether sulfone) solid polymer electrolytemembrane XIII of 42 μm in thickness. The ion electric conductivity ofthe obtained sulfohexamethylated poly(1,4-phenylene ether ether sulfone)solid polymer electrolyte membrane XIII was 40 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaidsulfohexamethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte membrane XIII and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, the ionelectric conductivity of the obtained solid polymer electrolyte membraneXIII was the same as its initial value like that of the perfluorocarbonsulfonic acid solid polymer electrolyte membrane (Nafion 117), and thesolid polymer electrolyte membrane XIII was firm.

On the other hand, as described in Comparative Example 2, (2), therelatively inexpensive sulfonated poly(1,4-phenylene ether ethersulfone) solid polymer electrolyte membrane X was broken to tattersunder the same conditions of hydrolysis by heating as above.

Thus, unlike the sulfonated poly(1,4-phenylene ether ether sulfone)solid polymer electrolyte membrane X, the inexpensivesulfohexamethylated poly(1,4-phenylene ether ether sulfone) solidpolymer electrolyte membrane XIII was stable like the perfluorocarbonsulfonic acid solid polymer electrolyte membrane (Nafion 117) and wasexcellent in both cost and resistance to hydrolysis (durability).

(4) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (3), i.e., a 5 wt % solution ofthe solid polymer electrolyte XIII in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution XIII).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution XIII and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution XIII after the maintenance was measured. As a result, it wasfound that the ion-exchange group equivalent weight of theelectrocatalyst-coating solution XIII was 660 g/equivalent, the samevalue as the initial value, namely, the electrocatalyst-coating solutionXIII was stable like the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution.

On the other hand, as described in Comparative Example 2, (2), theion-exchange group equivalent weight of the electrocatalyst-coatingsolution X was increased to 1,250 g/equivalent from its initial value of660 g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released.

Thus, unlike the inexpensive electrocatalyst-coating solution Xdescribed in Comparative Example 2, (2), the inexpensiveelectrocatalyst-coating solution XIII was stable like theperfluorocarbon sulfonic acid (Nation 117) electrocatalyst-coatingsolution and was excellent in both cost and resistance to hydrolysis(durability).

The aforesaid electrocatalyst-coating solution XIII was applied on bothsides of the solid polymer electrolyte membrane XIII obtained in theabove item (3), and was dried to produce a membrane-electrodes assemblyXIII having an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution X described in Comparative Example2, (2) was applied on both sides of the same solid polymer electrolytemembrane XIII as that obtained in the above item (3), and was dried toproduce a membrane-electrodes assembly XIII′ having an amount ofplatinum supported of 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte (Nafion 117) in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane XIII as thatobtained in the above item (3), and was dried to produce amembrane-electrodes assembly XIII″ having an amount of platinumsupported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XIII obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly XIII was not different from that before themaintenance like a membrane-electrodes assembly produced by using theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and the perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XIII′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly XIII′ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly XIII′ after themaintenance had power-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XIII″ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly XIII″ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly XIII″ after themaintenance had power-generating capability.

(5) Durability Test on Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies XIII, XIII′ and XIII″were allowed to absorb water by immersion in boiling deionized water for2 hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated. In detail, the singlecell for solid polymer electrolyte fuel cell shown in FIG. 1 wasproduced by adhering a packing material (a supporting current collector)5 of thin carbon paper to each of the electrodes of eachmembrane-electrodes assembly 4 obtained in Example 16 and composed of asolid polymer electrolyte membrane 1, an oxygen electrode 2 and ahydrogen electrode 3, and providing an electroconductive separator (abipolar plate) 6 capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material. The single cells for fuel cells thusobtained were subjected to a long-term deterioration test at a currentdensity of 300 mA/cm². The results obtained are shown in FIG. 16.

In FIG. 16, numerals 62, 63 and 64 indicate the results of thedurability test on the single cells for fuel cell obtained by using theassemblies XIII, XIII′ and XIII″, respectively, of the solid polymerelectrolyte membrane of the present invention and electrodes.

In FIG. 16, numeral 65 indicates the result of the durability test on asingle cell for fuel cell obtained by using the assembly of theperfluorocarbon sulfonic acid (Nafion 117) solid polymer electrolytemembrane and electrodes.

In FIG. 16, numeral 62 indicates the change with time of output voltageof the single cell for fuel cell of Example 16 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 63 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 16by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto. Numeral 64 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 16by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117).Numeral 65 indicates the change with time of output voltage of thesingle cell for fuel cell obtained by using the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117). Numeral 66indicates the change with time of output voltage of a single cell forfuel cell of Comparative Example 16 produced by using a solid polymerelectrolyte membrane of a polyether ether sulfone having sulfonic acidgroups directly bonded thereto and an electrocatalyst-coating solutioncontaining the polyether ether sulfone solid polymer electrolyte havingsulfonic acid groups directly bonded thereto.

As can be seen from the results indicated by numerals 62 and 64 in FIG.16, the initial voltage of the single cells obtained by using theassemblies XIII and XIII″, respectively, of the solid polymerelectrolyte membrane of the present invention and electrodes was 0.83 V,and the single cells had the same voltage as the initial voltage evenafter 5,000 hours of operation. These results were equal to thoseobtained by the use of the perfluorocarbon sulfonic acid solid polymerelectrolyte membrane (Nafion 117) and indicated by numeral 65 in FIG.16.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 66 in FIG. 16 (the single cell for fuelcell of Comparative Example 2 obtained by using the sulfonated aromatichydrocarbon solid polymer electrolyte X) was 0.73 V, and the output ofthis single cell was zero after 600 hours of operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte obtained bybonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte having sulfonic acid groups directly bondedthereto.

The single cell for fuel cell obtained by using the membrane-electrodesassembly XIII of the present invention is superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly XIII′. That is, the electrocatalyst-coating solution XIII ismore suitable than the electrocatalyst-coating solution X, for coatingan electrocatalyst for a membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 16 is higher than that of the single cell for fuel cell ofComparative Example 2 though the membrane-electrodes assemblies ofExample 16 and Comparative Example 2 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane and electrocatalyst-coating solutionused in the membrane-electrodes assembly of Example 16 is higher thanthat of the solid polymer electrolyte membrane andelectrocatalyst-coating solution used in the membrane-electrodesassembly of Comparative Example 2.

(6) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (5)according to the present invention. The fuel cell had an output of 3 kw.

As can be seen from Examples 15, 13, 14 and 16, the values of theion-exchange group equivalent weight (g/equivalent) of thesulfoalkylated poly(1,4-phenylene ether ether sulfone) solidelectrolytes in which the values of n (the number of carbon atoms of thealkylene group) are 1, 3, 4 and 6 are 650, 670, 650 and 660,respectively, which are substantially the same. The values of ionicconductance (S/cm) of the solid polymer electrolyte membranes obtainedby using these solid electrolytes are 5, 15, 25 and 40, respectively.

That is, with an increase of the value of n in the sulfoalkylatedaromatic hydrocarbon solid electrolytes, the ionic conductance and theproton transportability increase, so that an excellent solid polymerelectrolyte fuel cell can be obtained.

On the other hand, from the viewpoint of cost, the sulfopropylatedaromatic hydrocarbon solid polymer electrolyte and the sulfobutylatedaromatic hydrocarbon solid polymer electrolyte, which can be synthesizedby a one-stage reaction with a sultone, are more advantageous than thesulfohexamethylated aromatic hydrocarbon solid polymer electrolyte andthe sulfomethylated aromatic hydrocarbon solid polymer electrolyte,which are synthesized by a two-stage reaction.

That is, the value of n is preferably 3 or 4 for reconciling the ionicconductance and the cost.

EXAMPLE 17

(1) Synthesis of a sulfopropylated poly(1,6-naphthalene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 6.08 g(0.0155 mol) of a poly(1,5-naphthalene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-1-OC₁₀H₆-5-O—)_(n)] dried by its maintenance at 110°C. for 10 hours and 150 ml of dehydrated chloroform were placed in theflask and maintained at 60° C. for about 1 hour to effect dissolution.To the resulting solution was added 5.67 g (0.0464 mol) ofpropanesultone. Subsequently, 6.19 g (0.0464 mol) of anhydrous aluminumchloride thoroughly ground in a mortar was added thereto with stirringover a period of about 30 minutes. After completion of the addition ofanhydrous aluminum chloride, the resulting mixture was refluxed withstirring at 60° C. for 30 hours.

The polymer precipitated was filtered, washed with 150 ml of chloroformand then dried under reduced pressure. The dried polymer was suspendedin 250 ml of water and finely ground in a mixer, and the resultingfinely ground substance was filtered. This procedure was repeated fourtimes. After thorough washing with water, the water-insoluble finelyground substance thus obtained was dried at 90° C. under reducedpressure.

The dried substance was subjected to ¹HNMR measurement to find that newpeaks due to a —CH₂CH₂CH₂SO₃H group were present at 2.2 ppm and 3.8 ppm.This fact confirmed the introduction of sulfopropyl groups.

The sulfonic acid equivalent weight of the sulfopropylatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolyte XIVthus obtained was 770 g/equivalent.

Since the sulfopropylated poly(1,6-naphthalene ether ether sulfone)solid polymer electrolyte XIV can be produced through one step by usingthe poly(1,6-naphthalene ether ether sulfone), a relatively inexpensivecommercial engineering plastic, as a starting material, the cost ofproduction thereof is as low as less than one-fiftieth that of theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfopropylated poly(1,6-naphthalene ether ether sulfone) solid polymerelectrolyte XIV and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfopropylatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolyte XIVwas measured. As a result, it was found that the ion-exchange groupequivalent weight of the sulfopropylated poly(1,6-naphthalene etherether sulfone) solid polymer electrolyte XIV was 770 g/equivalent, thesame value as the initial value, namely, the solid polymer electrolyteXIV was stable like the perfluorocarbon sulfonic acid solid polymerelectrolyte (Nafion 117).

On the other hand, as described hereinafter in Comparative Example 3,(1), the ion-exchange group equivalent weight of an inexpensivesulfonated poly(1,6-naphthalene ether ether sulfone) solid polymerelectrolyte XV was increased to 1,300 g/equivalent from its initialvalue of 760 g/equivalent under the same conditions of hydrolysis byheating as above, namely, sulfonic acid groups were released from thesolid polymer electrolyte XV.

Thus, unlike the inexpensive sulfonated poly(1,6-naphthalene ether ethersulfone) solid polymer electrolyte XV described hereinafter inComparative Example 3, (1), the inexpensive sulfopropylatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolyte XIVwas stable like the perfluorocarbon sulfonic acid solid polymerelectrolyte (Nafion 117) and was excellent in both cost and resistanceto hydrolysis (durability).

(2) Formation of a Solid Polymer Electrolyte Membrane

The product obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membraneXIV of 25 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane XIV was 15 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane XIV obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, theion electric conductivity of the solid polymer electrolyte membrane XIVwas the same as its initial value like that of the perfluorocarbonsulfonic acid solid polymer electrolyte membrane (Nafion 117), and thesolid polymer electrolyte membrane XIV was firm.

On the other hand, as described hereinafter in Comparative Example 3,(2), the relatively inexpensive sulfonated aromatic hydrocarbon solidpolymer electrolyte membrane XV was broken to tatters under the sameconditions of hydrolysis by heating as above.

Thus, unlike the inexpensive sulfonated poly(1,6-naphthalene ether ethersulfone) solid polymer electrolyte membrane XV described hereinafter inComparative Example 3, (2), the inexpensive sulfopropylatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolytemembrane XIV was stable like the perfluorocarbon sulfonic acid solidpolymer electrolyte membrane (Nafion 117) and was excellent in both costand resistance to hydrolysis (durability).

(3) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte XIV in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution XIV).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution XIV and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution XIV after the maintenance was measured.

As a result, it was found that the ion-exchange group equivalent weightof the electrocatalyst-coating solution XIV was 760 g/equivalent, thesame value as the initial value, namely, the electrocatalyst-coatingsolution XIV was stable like the perfluorocarbon sulfonic acid (Nafion117) electrocatalyst-coating solution.

On the other hand, as described hereinafter in Comparative Example 3,(2), the ion-exchange group equivalent weight of theelectrocatalyst-coating solution XV was increased to 1,300 g/equivalentfrom its initial value of 760 g/equivalent under the same conditions ofhydrolysis by heating as above, namely, sulfonic acid groups werereleased.

Thus, unlike the inexpensive electrocatalyst-coating solution XVdescribed in Comparative Example 3, (2), the inexpensiveelectrocatalyst-coating solution XIV was stable like the perfluorocarbonsulfonic acid (Nafion 117) electrocatalyst-coating solution and wasexcellent in both cost and resistance to hydrolysis (durability).

The aforesaid electrocatalyst-coating solution XIV was applied on bothsides of the solid polymer electrolyte membrane XIV obtained in theabove item (2), and was dried to produce a membrane-electrodes assemblyXIV having an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution XV described hereinafter inComparative Example 3, (2) was applied on both sides of the same solidpolymer electrolyte membrane XIV as that obtained in the above item (2),and was dried to produce a membrane-electrodes assembly XIV′ having anamount of platinum supported of 0.25 mg/cm².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane XIV as thatobtained in the above item (2), and was dried to produce amembrane-electrodes assembly XIV″ having an amount of platinum supportedof 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XIV obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly XIV was not different from that before themaintenance like a membrane-electrodes assembly produced by using theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and the perfluorocarbon sulfonic acid solid polymer electrolyte(Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XIV′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly XIV′ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly XIV′ after themaintenance had power-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XIV″ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly XIV″ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly XIV″ after themaintenance had power-generating capability.

On the other hand, as described hereinafter in Comparative Example 3,(3), the membrane of a membrane-electrodes assembly XV produced by usingthe relatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane XV and the electrocatalyst-coating solution XV wasbroken to tatters and the electrodes of the assembly were peeled, underthe same conditions of hydrolysis by heating as above.

Thus, unlike the inexpensive membrane-electrodes assembly XV describedhereinafter in Comparative Example 3, (3), i.e., the assembly of thesulfonated aromatic hydrocarbon solid polymer electrolyte membrane andelectrodes, the inexpensive assembly XIV of the sulfopropylatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolytemembrane and electrodes was stable like the assembly of theperfluorocarbon sulfonic acid (Nafion 117) membrane and electrodes, andwas excellent in both cost and resistance to hydrolysis (durability).

(4) Durability Test on Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies XIV, XIV′ and XIV″were allowed to absorb water by immersion in boiling deionized water for2 hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated.

In detail, the single cell for solid polymer electrolyte fuel cell shownin FIG. 1 was produced by adhering a packing material (a supportingcurrent collector) 5 of thin carbon paper to each of the electrodes ofeach membrane-electrodes assembly 4 obtained in Example 17 and composedof a solid polymer electrolyte membrane 1, an oxygen electrode 2 and ahydrogen electrode 3, and providing an electroconductive separator (abipolar plate) 6 capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material. The single cells for fuel cells thusobtained were subjected to a long-term deterioration test at a currentdensity of 300 mA/cm². The results obtained are shown in FIG. 17.

In FIG. 17, numerals 67, 68 and 69 indicate the results of thedurability test on the single cells for fuel cell obtained by using theassemblies XIV, XIV′ and XIV″, respectively, of the solid polymerelectrolyte membrane of the present invention and electrodes.

In FIG. 17, numeral 70 indicates the result of the durability test on asingle cell for fuel cell obtained by using the assembly of theperfluorocarbon sulfonic acid (Nafion 117) solid polymer electrolytemembrane and electrodes.

In FIG. 17, numeral 67 indicates the change with time of output voltageof the single cell for fuel cell of Example 17 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 68 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 17by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto. Numeral 69 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 17by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117).Numeral 70 indicates the change with time of output voltage of thesingle cell for fuel cell obtained by using the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117). Numeral 71indicates the change with time of output voltage of a single cell forfuel cell of Comparative Example 17 produced by using a solid polymerelectrolyte membrane of a polyether ether sulfone having sulfonic acidgroups directly bonded thereto and an electrocatalyst-coating solutioncontaining the polyether ether sulfone solid polymer electrolyte havingsulfonic acid groups directly bonded thereto.

As can be seen from the results indicated by numerals 67 and 69 in FIG.17, the initial voltage of the single cells obtained by using theassemblies XIV and XIV″ respectively, of the solid polymer electrolytemembrane of the present invention and electrodes was 0.76 V, and thesingle cells had the same voltage as the initial voltage even after5,000 hours of operation. These results were equal to those obtained bythe use of the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and indicated by numeral 70 in FIG. 17.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 71 in FIG. 17 (the single cell for fuelcell obtained by using the sulfonated aromatic hydrocarbon solid polymerelectrolyte XV which is described hereinafter in Comparative Example 3)was 0.73 V, and the output of this single cell was zero after 600 hoursof operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte obtained bybonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte having sulfonic acid groups directly bondedthereto.

The single cell for fuel cell obtained by using the membrane-electrodesassembly XIV is superior in durability to the single cell for fuel cellobtained by using the membrane-electrodes assembly XIV′. That is, theelectrocatalyst-coating solution XIV is more suitable than theelectrocatalyst-coating solution XV, for coating an electrocatalyst fora membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 17 is higher than that of the single cell for fuel cell ofComparative Example 3 though the membrane-electrodes assemblies ofExample 17 and Comparative Example 3 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane and electrocatalyst-coating solutionused in the membrane-electrodes assembly of Example 17 is higher thanthat of the solid polymer electrolyte membrane andelectrocatalyst-coating solution used in the membrane-electrodesassembly of Comparative Example 3.

(5) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (4)according to the present invention. The fuel cell had an output of 3 kW.

Comparative Example 3

(1) Synthesis of a sulfonated poly(1,6-naphthalene ether ether sulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 3.22 g(0.0103 mol) of a poly(1,6-naphthalene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-1-OC₁₀H₆-5-O—)_(n)] dried by its maintenance at 110°C. for 10 hours and 100 ml of chloroform were placed in the flask andmaintained at 60° C. for about 1 hour to effect dissolution. To theresulting solution was added a solution of 1.165 g (0.01 mol) ofchlorosulfonic acid in 50 ml of 1,1,2,2-tetrachloroethane over a periodof about 10 minutes.

Subsequently, the resulting mixture was stirred at 60° C. for 4 hours,and the precipitate was filtered and then washed with 150 ml ofchloroform. The washed precipitate was dissolved in 250 ml of methanolat 60° C. The resulting solution was dried at 60° C. under reducedpressure. The polymer thus obtained was finely ground in a mixertogether with 250 ml of water, and the resulting mixture was filtered.This procedure was repeated three times.

The water-insoluble fine powder thus obtained was dried over phosphoruspentaoxide at 90° C. under reduced pressure. This fine powder wasinsoluble in water and soluble in methanol.

The dried fine powder was subjected to ¹HNMR measurement to find thatabsorptions at 7.3 to 8.0 ppm due to the hydrogen atoms of thenaphthalene rings and benzene rings in the starting poly(1,6-naphthaleneether ether sulfone) had been decreased, and that a new absorption dueto the hydrogen atom of a phenyl group adjacent to a SO₃H group waspresent at 8.3 ppm. This fact confirmed the introduction of sulfonicacid groups. The sulfonic acid equivalent weight of the sulfonatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolyte XVthus obtained was 760 g/equivalent.

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidsulfonated poly(1,6-naphthalene ether ether sulfone) solid polymerelectrolyte XV obtained and 20 ml of ion-exchanged water were maintainedat 120° C. for 2 weeks. After cooling and thorough washing with water,the ion-exchange group equivalent weight of the sulfonatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolyte XVwas measured. As a result, it was found that the sulfonic acidequivalent weight of the sulfonated poly(1,6-naphthalene ether ethersulfone) solid polymer electrolyte XV had been increased to 1,300g/equivalent from its initial value of 760 g/equivalent, namely,sulfonic acid groups had been released from the solid polymerelectrolyte XV.

(2) Formation of a Solid Polymer Electrolyte Membrane

The sulfonated poly(1,6-naphthalene ether ether sulfone) solid polymerelectrolyte XV obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membrane XVof 45 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane XV was 8 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane XV obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. As a result, the solidpolymer electrolyte membrane XV was broken to tatters.

(3) Production of an Electrocatalyst-coating Solution and aMembrane-electrodes Assembly

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte XV in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution XV).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution XV and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution XV after the maintenance was measured. As a result, it wasfound that the ion-exchange group equivalent weight of theelectrocatalyst-coating solution XV had been increased to 1,300g/equivalent from its initial value of 760 g/equivalent, namely,sulfonic acid groups had been released.

The aforesaid electrocatalyst-coating solution XV was applied on bothsides of the solid polymer electrolyte membrane XV obtained in the aboveitem (2), and was dried to produce a membrane-electrodes assembly XVhaving an amount of platinum supported of 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XV obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. As a result, the membraneof the membrane-electrodes assembly XV was broken to tatters and itselectrodes were peeled.

(4) Durability Test on a Single Cell for Fuel Cell

A single cell for solid polymer electrolyte fuel cell was produced byadhering a packing material (a supporting current collector) of thincarbon paper to each side of the membrane-electrodes assembly XV ofComparative Example 3, and providing an electroconductive separator (abipolar plate) capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material. The single cell was subjected to along-term operation test at a current density of 300 mA/cm². As aresult, it was found that as indicated by numeral 71 in FIG. 17, theinitial output voltage of the single cell was 0.73 V and that the outputvoltage of the single cell was zero after 600 hours of operation.

EXAMPLE 18

(1) Synthesis of a Sulfobutylated poly(1,6-naphthalene ether ethersulfone)

The inner atmosphere of a 500-ml four-necked round bottom flask equippedwith a stirrer, a thermometer and a reflux condenser having a calciumchloride tube connected thereto was replaced with nitrogen. Then, 6.08 g(0.0155 mol) of a poly(1,5-naphthalene ether ether sulfone)[(—C₆H₄-4-SO₂C₆H₄-1-OC₁₀H₆-5-O—)_(n)] dried by its maintenance at 110°C. for 10 hours and 150 ml of dehydrated chloroform were placed in theflask and maintained at 60° C. for about 1 hour to effect dissolution.To the resulting solution was added 6.26 g (0.0464 mol) ofbutanesultone.

Subsequently, 6.19 g (0.0464 mol) of anhydrous aluminum chloridethoroughly ground in a mortar was added thereto with stirring over aperiod of about 30 minutes. After completion of the addition ofanhydrous aluminum chloride, the resulting mixture was refluxed withstirring at 60° C. for 30 hours. The polymer precipitated was filtered,washed with 150 ml of chloroform and then dried under reduced pressure.The dried polymer was suspended in 250 ml of water and finely ground ina mixer, and the resulting finely ground substance was filtered. Thisprocedure was repeated four times. After thorough washing with water,the water-insoluble finely ground substance thus obtained was dried at90° C. under reduced pressure.

The dried substance was subjected to ¹HNMR measurement to find that newpeaks due to a —CH₂CH₂CH₂CH₂SO₃H group were present at 2.2 ppm and 3.8ppm. This fact confirmed the introduction of sulfobutyl groups. Thesulfonic acid equivalent weight of the sulfobutylatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolyte XVIthus obtained was 770 g/equivalent.

Since the sulfobutylated poly(1,6-naphthalene ether ether sulfone) solidpolymer electrolyte XVI can be produced through one step by using thepoly(1,6-naphthalene ether ether sulfone), a relatively inexpensivecommercial engineering plastic, as a starting material, the cost ofproduction thereof is as low as less than one-fiftieth that of theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117)produced through five steps by using an expensive starting material.

In a Teflon-coated closed container made of SUS, 1.0 g of the obtainedsulfobutylated poly(1,6-naphthalene ether ether sulfone) solid polymerelectrolyte XVI and 20 ml of ion-exchanged water were maintained at 120°C. for 2 weeks. After cooling and thorough washing with water, theion-exchange group equivalent weight of the sulfobutylatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolyte XVIwas measured.

As a result, it was found that the ion-exchange group equivalent weightof the sulfobutylated poly(1,6-naphthalene ether ether sulfone) solidpolymer electrolyte XVI was 750 g/equivalent, the same value as theinitial value, namely, the solid polymer electrolyte XVI was stable likethe perfluorocarbon sulfonic acid solid polymer electrolyte (Nafion117).

On the other hand, as described in Comparative Example 3, (1), theion-exchange group equivalent weight of the inexpensive sulfonatedpoly(1,6-naphthalene ether ether sulfone) solid polymer electrolyte XVwas increased to 1,300 g/equivalent from its initial value of 760g/equivalent under the same conditions of hydrolysis by heating asabove, namely, sulfonic acid groups were released from the solid polymerelectrolyte XV.

Thus, unlike the inexpensive sulfonated poly(1,6-naphthalene ether ethersulfone) solid polymer electrolyte XV described in Comparative Example3, (1), the inexpensive sulfobutylated poly(1,6-naphthalene ether ethersulfone) solid polymer electrolyte XVI was stable like theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117) andwas excellent in both cost and resistance to hydrolysis (durability).

(2) Formation of a Solid Polymer Electrolyte Membrane

The product obtained in the above item (1) was dissolved in aN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solvent(volume ratio; 20:80:25) to a concentration of 5 wt %. The resultingsolution was spread on a glass plate by spin coating, air-dried and thendried in vacuo at 80° C. to form a solid polymer electrolyte membraneXVI of 25 μm in thickness. The ion electric conductivity of the obtainedsolid polymer electrolyte membrane XVI was 25 S/cm.

In a Teflon-coated closed container made of SUS, the aforesaid solidpolymer electrolyte membrane XVI and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. After the maintenance, the ionelectric conductivity of the solid polymer electrolyte membrane XVI wasthe same as its initial value like that of the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117), and the solidpolymer electrolyte membrane XVI was firm.

On the other hand, as described in Comparative Example 3, (2), therelatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane XV was broken to tatters under the same conditionsof hydrolysis by heating as above. Thus, unlike the inexpensivesulfonated poly(1,6-naphthalene ether ether sulfone) solid polymerelectrolyte membrane XV described in Comparative Example 3, (2), theinexpensive sulfobutylated poly(1,6-naphthalene ether ether sulfone)solid polymer electrolyte membrane XVI was stable like theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and was excellent in both cost and resistance to hydrolysis(durability).

(3) Production of Electrocatalyst-coating Solutions andMembrane-electrodes Assemblies

The same solution as in the above item (2), i.e., a 5 wt % solution ofthe solid polymer electrolyte XVI in theN,N-dimethylformamide-cyclohexanone-methyl ethyl ketone mixed solventwas added to platinum-supporting carbon (content of platinum supported:40 wt %), so that the weight ratio of platinum catalyst to the solidpolymer electrolyte might be 2:1. The platinum-supporting carbon wasuniformly dispersed in the solution to prepare a paste (anelectrocatalyst-coating solution XVI).

In a Teflon-coated closed container made of SUS, 1.0 g of the aforesaidelectrocatalyst-coating solution XVI and 20 ml of ion-exchanged waterwere maintained at 120° C. for 2 weeks. After cooling, the solvent wasvaporized and the resulting solid was washed with water. Then, theion-exchange group equivalent weight of the electrocatalyst-coatingsolution XVI after the maintenance was measured.

As a result, it was found that the ion-exchange group equivalent weightof the electrocatalyst-coating solution XVI was 750 g/equivalent, thesame value as the initial value, namely, the solution XVI was stablelike the perfluorocarbon sulfonic acid (Nafion 117)electrocatalyst-coating solution.

On the other hand, as described in Comparative Example 3, (2), theion-exchange group equivalent weight of the electrocatalyst-coatingsolution XV was increased to 1,300 g/equivalent from its initial valueof 760 g/equivalent under the same conditions of hydrolysis by heatingas above, namely, sulfonic acid groups were released.

Thus, unlike the inexpensive electrocatalyst-coating solution XVdescribed in Comparative Example 3, (2), the inexpensiveelectrocatalyst-coating solution XVI was stable like the perfluorocarbonsulfonic acid (Nafion 117) electrocatalyst-coating solution and wasexcellent in both cost and resistance to hydrolysis (durability).

The aforesaid electrocatalyst-coating solution XVI was applied on bothsides of the solid polymer electrolyte membrane XVI obtained in theabove item (2), and was dried to produce a membrane-electrodes assemblyXVI having an amount of platinum supported of 0.25 mg/cm².

The electrocatalyst-coating solution XV described in Comparative Example3, (2) was applied on both sides of the same solid polymer electrolytemembrane XVI as that obtained in the above item (2), and was dried toproduce a membrane-electrodes assembly XVI′ having an amount of platinumsupported of 0.25 mg/cm ².

A 5 wt % solution of the perfluorocarbon sulfonic acid solid polymerelectrolyte in an alcohol-water mixed solvent was added toplatinum-supporting carbon (content of platinum supported: 40 wt %), sothat the weight ratio of platinum catalyst to the solid polymerelectrolyte might be 2:1. The platinum-supporting carbon was uniformlydispersed in the solution to prepare a paste (an electrocatalyst-coatingsolution). This electrocatalyst-coating solution was applied on bothsides of the same solid polymer electrolyte membrane XVI as thatobtained in the above item (2), and was dried to produce amembrane-electrodes assembly XVI″ having an amount of platinum supportedof 0.25 mg/cm².

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XVI obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. After the maintenance, themembrane-electrodes assembly XVI was not different from that before themaintenance like a membrane-electrodes assembly produced at a high costby using the perfluorocarbon sulfonic acid solid polymer electrolytemembrane (Nafion 117) and the perfluorocarbon sulfonic acid solidpolymer electrolyte (Nafion 117), and its membrane was firm.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XVI′ obtained and 20 ml of ion-exchangedwater were maintained at 120° C. for 2 weeks. In the membrane-electrodesassembly XVI′ after the maintenance, the electrodes were peeling alittle but the membrane was firm. The assembly XVI′ after themaintenance had power-generating capability.

In a Teflon-coated closed container made of SUS, the aforesaidmembrane-electrodes assembly XVI″ and 20 ml of ion-exchanged water weremaintained at 120° C. for 2 weeks. In the membrane-electrodes assemblyXVI″ after the maintenance, the electrodes were peeling a little but themembrane was firm. The assembly XVI″ after the maintenance hadpower-generating capability.

On the other hand, as described in Comparative Example 3, (3), themembrane of the membrane-electrodes assembly XV produced by using therelatively inexpensive sulfonated aromatic hydrocarbon solid polymerelectrolyte membrane XV and the electrocatalyst-coating solution XV wasbroken to tatters and the electrodes of the assembly were peeled, underthe same conditions of hydrolysis by heating as above.

Thus, unlike the inexpensive membrane-electrodes assembly XV describedin Comparative Example 3, (3), i.e., the assembly of the sulfonatedaromatic hydrocarbon solid polymer electrolyte membrane and electrodes,the inexpensive assembly XVI of the sulfobutylated poly(1,6-naphthaleneether ether sulfone) solid polymer electrolyte membrane and electrodeswas stable like the assembly of the perfluorocarbon sulfonic acid(Nafion 117) membrane and electrodes, and was excellent in both cost andresistance to hydrolysis (durability).

(4) Durability Test on Single Cells for Fuel Cell

The above-mentioned membrane-electrodes assemblies XVI, XVI′ and XVI″were allowed to absorb water by immersion in boiling deionized water for2 hours. Each of the thus treated membrane-electrodes assemblies wasincorporated into a cell for evaluation and the output capability of theresulting single cell for fuel cell was evaluated.

In detail, the single cell for solid polymer electrolyte fuel cell shownin FIG. 1 was produced by adhering a packing material (a supportingcurrent collector) 5 of thin carbon paper to each of the electrodes ofeach membrane-electrodes assembly 4 obtained in Example 18 and composedof a solid polymer electrolyte membrane 1, an oxygen electrode 2 and ahydrogen electrode 3, and providing an electroconductive separator (abipolar plate) 6 capable of serving as a separator between electrodechambers and passageways for gas supply to the electrodes, on the outersurface of each packing material. The single cells for fuel cells thusobtained were subjected to a long-term deterioration test at a currentdensity of 300 mA/cm². The results obtained are shown in FIG. 18.

In FIG. 18, numerals 72, 73 and 74 indicate the results of thedurability test on the single cells for fuel cell obtained by using theassemblies XVI, XVI′ and XVI″, respectively, of the solid polymerelectrolyte membrane of the present invention and electrodes. In FIG.18, numeral 75 indicates the result of the durability test on a singlecell for fuel cell obtained by using the assembly of the perfluorocarbonsulfonic acid (Nafion 117) solid polymer electrolyte membrane andelectrodes.

In FIG. 18, numeral 72 indicates the change with time of output voltageof the single cell for fuel cell of Example 18 produced by using a solidpolymer electrolyte membrane of a polyether ether sulfone havingsulfonic acid groups bonded thereto through alkylene groups and anelectrocatalyst-coating solution containing the polyether ether sulfonesolid polymer electrolyte having sulfonic acid groups bonded theretothrough alkylene groups. Numeral 73 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 18by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing a polyetherether sulfone solid polymer electrolyte having sulfonic acid groupsdirectly bonded thereto. Numeral 74 indicates the change with time ofoutput voltage of the single cell for fuel cell produced in Example 18by using a solid polymer electrolyte membrane of the polyether ethersulfone having sulfonic acid groups bonded thereto through alkylenegroups and an electrocatalyst-coating solution containing theperfluorocarbon sulfonic acid solid polymer electrolyte (Nafion 117).Numeral 75 indicates the change with time of output voltage of thesingle cell for fuel cell obtained by using the perfluorocarbon sulfonicacid solid polymer electrolyte membrane (Nafion 117). Numeral 76indicates the change with time of output voltage of a single cell forfuel cell of Comparative Example 18 produced by using a solid polymerelectrolyte membrane of a polyether ether sulfone having sulfonic acidgroups directly bonded thereto and an electrocatalyst-coating solutioncontaining the polyether ether sulfone solid polymer electrolyte havingsulfonic acid groups directly bonded thereto.

As can be seen from the results indicated by numerals 72 and 74 in FIG.18, the initial voltage of the single cells obtained by using theassemblies XVI and XVI″, respectively, of the solid polymer electrolytemembrane and electrodes was 0.79 V, and the single cells had the samevoltage as the initial voltage even after 5,000 hours of operation.These results were equal to those obtained by the use of theperfluorocarbon sulfonic acid solid polymer electrolyte membrane (Nafion117) and indicated by numeral 75 in FIG. 18.

On the other hand, the initial output voltage of the single cell forfuel cell indicated by numeral 76 in FIG. 18 (the single cell for fuelcell of Comparative Example 3 obtained by using the sulfonated aromatichydrocarbon solid polymer electrolyte XV) was 0.73 V, and the output ofthis single cell was zero after 600 hours of operation.

From this fact, it is clear that the single cell for fuel cell producedby using the aromatic hydrocarbon solid polymer electrolyte obtained bybonding sulfonic acid groups to the aromatic rings of an aromatichydrocarbon polymer through alkylene groups is superior in durability tothe single cell for fuel cell produced by using the aromatic hydrocarbonsolid polymer electrolyte having sulfonic acid groups directly bondedthereto.

The single cell for fuel cell obtained by using the membrane-electrodesassembly XVI of the present invention is superior in durability to thesingle cell for fuel cell obtained by using the membrane-electrodesassembly XVI′. That is, the electrocatalyst-coating solution XVI is moresuitable than the electrocatalyst-coating solution XV, for coating anelectrocatalyst for a membrane-electrodes assembly.

The reason why the output voltage of the single cell for fuel cell ofExample 18 is higher than that of the single cell for fuel cell ofComparative Example 3 though the membrane-electrodes assemblies ofExample 18 and Comparative Example 3 have the same amount of platinumsupported of 0.25 mg/cm², is that the ion electric conductivity of thesolid polymer electrolyte membrane and electrocatalyst-coating solutionused in the membrane-electrodes assembly of Example 18 is higher thanthat of the solid polymer electrolyte membrane andelectrocatalyst-coating solution used in the membrane-electrodesassembly of Comparative Example 3.

(5) Production of a Fuel Cell

A solid polymer electrolyte fuel cell was produced by laminating 36single cells produced in the same manner as in the above item (4)according to the present invention. The fuel cell had an output of 3 kw.

As can be seen from Examples 3 and 4, the initial output voltage of asingle cell for fuel cell obtained by using a sulfoalkylated polyetherether sulfone solid electrolyte having a sulfonic acid equivalent weightof 530 to 970 g/equivalent is equal to or higher than the output voltageof a single cell for fuel cell obtained by using the perfluorocarbonsulfonic acid (Nafion 117) membrane. The former single cell for fuelcell is especially preferable because it is not deteriorated even whenoperated for 5,000 hours.

As can be seen from the items (1) and (2) in Examples 11, 9, 10 and 12,the values of the ion-exchange group equivalent weight (g/equivalent) ofthe sulfoalkylated poly(1,4-biphenylene ether ether sulfone) solidelectrolytes of the formula [3] in which the values of n (the number ofcarbon atoms of the alkylene group) are 1, 3, 4 and 6 are 660, 680, 670and 670, respectively, which are substantially the same. The values ofionic conductance (S/cm) of the solid polymer electrolyte membranesobtained by using these solid electrolytes are 7, 15, 25 and 35,respectively.

As can be seen from Examples 15, 13, 14 and 16, the values of theion-exchange group equivalent weight (g/equivalent) of thesulfoalkylated poly(1,4-phenylene ether ether sulfone) solidelectrolytes in which the values of n (the number of carbon atoms of thealkylene group) are 1, 3, 4 and 6 are 650, 670, 650 and 660,respectively, which are substantially the same. The values of ionicconductance (S/cm) of the solid polymer electrolyte membranes obtainedby using these solid electrolytes are 5, 15, 25 and 40, respectively.

That is, with an increase of the value of n in the sulfoalkylatedaromatic carbon solid electrolytes, the ionic conductance and the protontransportability increase, so that an excellent solid polymerelectrolyte fuel cell can be obtained.

On the other hand, from the viewpoint of cost, the sulfopropylatedaromatic hydrocarbon solid polymer electrolytes and the sulfobutylatedaromatic hydrocarbon solid polymer electrolytes, which can besynthesized by a one-stage reaction with a sultone, are moreadvantageous than the sulfohexamethylated aromatic hydrocarbon solidpolymer electrolytes and the sulfomethylated aromatic hydrocarbon solidpolymer electrolytes, which are synthesized by a two-stage reaction.That is, the value of n is preferably 3 or 4 for reconciling the ionicconductance and the cost.

Since the present inventive polyether ether sulfone having sulfonic acidgroups introduced thereinto through alkylene groups can be producedthrough one or two steps by using an inexpensive engineering plastic asa starting material, the cost of production thereof is as very low asless than one-thirtieth that of a fluorine-containing solid polymerelectrolyte membrane represented by the perfluorocarbon sulfonic acidmembranes produced through five steps by using an expensive startingmaterial.

Thus, unlike bonding of sulfonic acid groups directly to the aromaticrings, bonding of sulfonic acid groups to the aromatic rings throughalkylene groups gives a high ion electric conductivity, prevents therelease of the sulfonic acid groups even in the presence of a strongacid and at a high temperature, and permits attainment of a highdurability sufficient for practical purposes and reduction of the cost.

It should be further understood by those skilled in the art thatalthough the foregoing description has been made on embodiments of theinvention, the invention is not limited thereto and various changes andmodifications may be made without departing from the spirit of theinvention and the scope of the appended claims.

1. A solid polymer electrolyte comprising a polyether ether sulfone usedas an electrolyte, said polyether ether sulfone having sulfoalkyl groupsbonded thereto and represented by the formula [1]:—(CH₂)_(n)—SO₃H  [1] wherein n is an integer of 1 to
 6. 2. A solidpolymer electrolyte according to claim 1, wherein the polyether ethersulfone is represented by the formula [2]:

wherein n is an integer of 1 to 6, each of m, a and b is an integer of 0to 4, provided that m, a and b are not 0 at the same time, x is aninteger of 1 to 3, y is an integer of 1 to 5, and Ar is an aromaticresidue.
 3. A solid polymer electrolyte according to claim 1, whereinthe polyether ether sulfone is represented by the formula [3]:

wherein n is an integer of 1 to 6, and each of a, b, c and d is aninteger of 0 to 4, provided that a, b, c and d are not 0 at the sametime.
 4. A solid polymer electrolyte according to claim 1, wherein thepolyether ether sulfone is represented by the formula [4]:

wherein each of a, b, c and d is an integer of 0 to 4, provided that a,b, c and d are not 0 at the same time.
 5. A solid polymer electrolyteaccording to claim 1, wherein the polyether ether sulfone is representedby the formula [5]:

wherein each of a, b, c and d is an integer of 0 to 4, provided that a,b, c and d are not 0 at the same time.
 6. A solid polymer electrolyteaccording to claim 1, wherein the polyether ether sulfone is representedby the formula [6]:

wherein n is an integer of 1 to 6, and each of a, b and c is an integerof 0 to 4, provided that a, b and c are not 0 at the same time.
 7. Asolid polymer electrolyte according to claim 1, wherein the polyetherether sulfone is represented by the formula [7]:

wherein each of a, b and c is an integer of 0 to 4, provided that a, band c are not 0 at the same time.
 8. A solid polymer electrolytecomprising a polyether ether sulfone having sulfonic acid groups bondedthereto through alkylene groups, said polyether ether sulfone being usedas an electrolyte and represented by the formula [8]:

wherein each of a, b and c is an integer of 0 to 4, provided that a, band c are not 0 at the same time.
 9. A solid polymer electrolyteaccording to claim 1, wherein the polyether ether sulfone is representedby the formula [9]:

wherein each of a, b, c and d is an integer of 0 to 4, provided that a,b, c and d are mot 0 at the same time.
 10. A solid polymer electrolyteaccording to claim 1, which has an ion-exchange group equivalent weightof 530 to 970 g/equivalent.